Antiviral articles

ABSTRACT

Provided is a textile made of filament yarn comprising a polymer composition that is durable and reusable having permanent or near-permanent antiviral properties and that includes a polymer, a metal ion, preferably a zinc and/or copper ion, and an optional phosphorus compound, wherein fibers and/or fabric formed from the polymer composition demonstrate antiviral properties and wherein the polymer is hygroscopic. The present disclosure also describes methods of forming the polymer compositions and methods of preparing fibers from the polymer composition.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/985,091, filed Mar. 4, 2020, U.S. Provisional Application No.63/000,717, filed Mar. 27, 2020, U.S. Provisional Application No.63/105,051, filed Oct. 23, 2020, each of which is incorporated herein byreference.

FIELD

The present disclosure relates to an antiviral article having aneffective amount of metal ions incorporated within a hygroscopic polymerto deactivate viruses. The antiviral property of the article is robust,durable, and/or washable which may allow the article to be reusable.

BACKGROUND

There is a growing interest in fabrics having antiviral and/orantimicrobial properties. In an attempt to achieve such properties,conventional techniques have applied a number of treatments or coatingsto fibers to impart antimicrobial properties to fabrics. Compoundscontaining copper, silver, gold, or zinc, either individually or incombination, have been used in these applications—typically in the formof a topical coating treatment—to effectively combat pathogens such asbacteria, mold, mildew, virus, spores, and fungus. These types ofantimicrobial fibers and fabrics may be used in many industriesincluding healthcare, hospitality, military, and athletics, amongothers. However, these coated fibers have not demonstrated adequatelypermanent antiviral properties. Furthermore, these coated fibers andfabrics have struggled to meet many other requirements of theseapplications.

For example, in the healthcare and hospitality industries, certainfabrics are required to be sanitary at all times. To comply with thesesanitation standards, the fabrics are subject to daily washing and,often times, bleaching. Thus, in many applications repeated cycles ofuse, washing, or soaking are quite common. Unfortunately, conventionalfibers and fabrics have been found to deteriorate and lose antiviraland/or antimicrobial properties during repeated uses and/or wash cycles.

Additionally, many of the conventional antimicrobial fabrics do notdemonstrate sufficient antiviral and/or antimicrobial properties, nor dothey retain these properties when the fabrics are dyed. Fabrics areoften dyed with or in various colors by submerging the fabric in a dyebath. In many cases, however, antimicrobial additives are extracted fromthe fibers/fabric, e.g., during dyeing operations, which causes theantimicrobial properties to deteriorate. Further, the antimicrobialtreatments/coatings that may be extracted from conventional fabrics mayhave undesired environmental consequences.

As one example of conventional antimicrobial yarns and fabrics, U.S.Pat. No. 6,584,668 discloses durable non-electrically conductive metaltreatments applied to yarns and textile fabrics. The durablenon-electrically conductive metal treatments are coatings or finishesapplied to yarns and textile fabrics. The metal treatments may includesilver and/or silver ions, zinc, iron, copper, nickel, cobalt, aluminum,gold, manganese, magnesium, and the like. The metal treatments areapplied to the exterior surface of the yarn or fabric as a coating orfilm.

Some synthetic fibers having antimicrobial fibers are also known in theart. For example, U.S. Pat. No. 4,701,518 discloses an antimicrobialnylon prepared in water with a zinc compound phosphorus compound to formcarpet fibers. The process produces nylon fibers for carpets having 18denier per filament (dpf), and are prepared by conventional meltpolymerization. Such carpet fibers typically have average diameters thatare well above 30 microns, which are generally unsuitable fornext-to-skin applications. Furthermore, the conventional additives addedto polymer compositions to impart antimicrobial properties in thesynthetic fibers made therefrom have been found to reduce the relativeviscosity in the polymer compositions. This reduced relative viscosityproduces further difficulty in producing synthetic fibers from thepolymer composition, e.g., increased difficulty in extruding the polymercomposition.

As another example, US Publication No. 2020/0102673 disclosesantimicrobial fibers that include antimicrobial nanoparticles dispersedsubstantially uniformly in a polymer matrix. Textiles and othermaterials can be formed from such fibers. The fibers may be formed via amasterbatch process or in a process wherein the antimicrobialnanoparticles, polymeric component, and additive(s) are melt processedtogether directly. Devices can be at least partially formed from polymermaterials that include antimicrobial nanoparticles dispersedsubstantially uniformly in a polymer matrix.

Also, U.S. Pat. No. 10,201,198 discloses a protective mask with anultrafine fibrous coating. The ultrafine fibrous coating includespartially gelled submicron fibers interweaved with nanofibers and abiocide encapsulated in, surface-attached onto, blended with, physicallytrapped, and/or chemically linked to the submicron fibers andnanofibers. In an example, a microfibrous substrate with the coatingassembles with other microfibrous substrates to form a protective maskhaving N95 level of protection and bacteria-killing capability.

Although some references may teach the use of antimicrobial fibers andfabrics, a need exists for antiviral polymer compositions that retainantiviral properties, e.g., have improved antiviral retention rates,and/or resistance to the extraction of antiviral additives therefrom,while also being able to achieve thinner fiber diameters and/or denier.There is a further need for antiviral polymer compositions suitableproducing high-contact products, which may contribute to transmission ofviruses.

SUMMARY

In some cases, the present disclosure relates to an antiviral articlecomprising a textile that is durable, washable, reusable and has aneffective amount of one or more metal ions. Textile may be a woven orknitted textile. Several end use are described herein for the article,and these uses include but are not limited to a mask, wipe, gown, towel,protective clothing, or protective net. In some cases, the presentdisclosure relates to an antiviral article comprising a textile having abasis weight of greater than or equal to 15 grams per square meter(gsm), e.g., from 15 to 320 gsm, the textile comprising filament yarncomprising one or more hygroscopic polymers each having an average fiberdiameter from 1 to 20 microns, e.g., from 10 to 20 microns, and aneffective amount of one or more metal ions incorporated within the oneor more hygroscopic polymers for deactivating viruses exposed to thearticle. In one embodiment, the concentration of the one or more metalions is greater than or equal to 200 wppm, e.g., from 200 wppm to 1,000wppm. Hygroscopic polymers may comprise a polyamide, polyurethane,polycarbonate, polyesters, polyacrylates, or acrylonitrile butadienestyrene, and preferably comprise at least polyamide. The polyamide maybe a reaction product of at least one C₄ to C₁₆ aliphatic dicarboxylicacid, cyclo dicarboxylic acid, or aromatic dicarboxylic acid and atleast one alkylene diamine having from 2 to 16 carbon atoms or anaromatic diamine. The hygroscopic polymers absorbs more than 0.3% ofmoisture based on the weight of the hygroscopic polymer. The metal ionsmay comprise zinc, copper, or silver in an effective amount. Theconcentration of the one or more metal ions may exceed the concentrationof one or more metal compounds, which may comprise oxides, carbonates,stearates, pyrithiones, or adipates. In some embodiments, the article isreusable and the article has a metal ion retention rate of greater thanor equal to 65%. The one or more metal ions are effective atdeactivating several different types of viruses, including adenovirus, aherpesvirus, a poxvirus, a rhinovirus, a coxsackievirus, an enterovirus,a morbillivirus, a coronavirus, an influenza A virus, an avian influenzavirus, a swine-origin influenza virus, or an equine influence virus. Theeffective of the one or more metal ions provides that the exhibits atleast a 1-log reduction of virus, including human coronavirus, H1N1, orSars-CoV-2, after a period of 60 minutes according to ISO 18184:2019. Insome embodiments, the filament yarn may comprises an phosphorus compoundand wherein the phosphorus compound comprises benzene phosphinic acid,phosphorous acid, or manganese hypophosphite, or combinations thereof.When the metal ion is a zinc ion and wherein the molar ratio of thephosphorus to the zinc ranges from 0.01:1 to 3:1.

In some cases, the present disclosure relates to an antiviral articlecomprising a textile having a basis weight of greater than or equal to15 grams per square meter (gsm), e.g., from 15 to 320 gsm, the textilecomprising filament yarn comprising a polyamide having an average fiberdiameter from 1 to 20 microns, e.g., from 10 to 20 microns, and aneffective amount of one or more metal ions incorporated within thepolyamide for deactivating viruses exposed to the article. The polyamidemay be a reaction product of at least one C₄ to C₁₆ aliphaticdicarboxylic acid, cyclo dicarboxylic acid, or aromatic dicarboxylicacid and at least one alkylene diamine having from 2 to 16 carbon atomsor an aromatic diamine. Preferred polyamides include PA-4T/4I; PA-4T/6I;PA-5T/5I; PA-6; PA-6,6; PA-6,6/6; PA-10; PA-12; PA-6,10; PA-6,12;PA-6,6/6T; PA-6T/6I; PA-6T/6I/6; PA-6T/6; PA-6T/6I/66; PA-6T/MPMDT;PA-6T/66; PA-6T/610; PA-10T/612; PA-10T/106; PA-6T/612; PA-6T/10T;PA-6T/10I; PA-9T; PA-10T; PA-12T; PA-10T/10I; PA-10T/12; PA-10T/1I;PA-6T/9T; PA-6T/12T; PA-6T/10T/6I; PA-6T/6I/6; PA-6T/6I/12; andcopolymers, blends, mixtures and/or other combinations thereof. Themetal ions may comprise zinc, copper, or silver in an effective amount,and preferably comprise zinc ions (Zn 2+). The concentration of the oneor more metal ions may exceed the concentration of one or more metalcompounds, which may comprise oxides, carbonates, stearates,pyrithiones, or adipates. In some embodiments, the article is reusableand the article has a metal ion retention rate of greater than or equalto 65%. The one or more metal ions are effective at deactivating severaldifferent types of viruses, including adenovirus, a herpesvirus, apoxvirus, a rhinovirus, a coxsackievirus, an enterovirus, amorbillivirus, a coronavirus, an influenza A virus, an avian influenzavirus, a swine-origin influenza virus, or an equine influence virus. Theeffective of the one or more metal ions provides that the exhibits atleast a 1-log reduction of virus, including human coronavirus, H1N1, orSars-CoV-2, after a period of 60 minutes according to ISO 18184:2019. Insome embodiments, the filament yarn may comprises an phosphorus compoundand wherein the phosphorus compound comprises benzene phosphinic acid,phosphorous acid, or manganese hypophosphite, or combinations thereof.When the metal ion is a zinc ion and wherein the molar ratio of thephosphorus to the zinc ranges from 0.01:1 to 3:1.

In some embodiments, the present invention is directed to antiviralfilament yarn comprising one or more hygroscopic polymers, preferablypolyamide, each having an average fiber diameter from 1 to 20 micron,and an effective amount of one or more metal ions incorporated withinthe one or more hygroscopic polymers for deactivating viruses exposed tothe yarn. The filament yarn may be woven or knitted into a textile. Inone embodiment, the concentration of the one or more metal ions isgreater than or equal to 200 wppm, e.g., from 200 wppm to 1,000 wppm. Inone embodiment, the concentration of the one or more metal ions isgreater than or equal to 200 wppm, e.g., from 200 wppm to 1,000 wppm.Although polyamide is preferred, the hygroscopic polymer may alsocomprise polyurethane, polycarbonate, polyesters, polyacrylates, oracrylonitrile butadiene styrene. In one embodiment, the filament yarncomprises linear denier per filament less than or equal to 12 dpf, e.g.,from 1 dpf to 12 dpf.

BRIEF DESCRIPTION OF THE DRAWINGS

The following is a brief description of the drawings, which arepresented for the purposes of illustrating the exemplary embodimentsdisclosed herein and not for the purposes of limiting the same.

FIG. 1A is graph showing the liquid retention for fabrics described inExample 1;

FIG. 1B is graph showing the liquid retention on a dry weight basis forfabrics described in Example 1;

FIG. 1C is graph showing the virus retention for fabrics described inExample 1;

FIGS. 1D and 1E are graphs for the virus recovery for the fabricsdescribed in Example 1;

FIG. 2A are plaque assays showing the effect of different zinc chlorideand EDTA concentrations on IAV titers as described in Example 2;

FIG. 2B is a graph showing the cytotoxicity of zinc chloride and EDTA inMDCK cells as described in Example 2;

FIG. 2C is a Western blot of IAV HA and NP protein levels after exposureto zinc chloride and neutralization with EDTA as described in Example 2;

FIG. 2D is a graph of the HA:NP protein levels reported in Example 2;

FIG. 2E is a graph showing the NA segment Rt-qPCR analysis of IAV virusafter exposure to zinc chloride and neutralization with EDTA;

FIGS. 3A and 3B are graphs showing the virus deactivation of the fabricreported in Example 3;

FIG. 3C is a Western blot for the viral reduction show the graph in FIG.3D for the fabric reported in Example 3;

FIG. 3E is a Western blot for the viral reduction show the graph in FIG.3F for the fabric reported in Example 3; and

FIGS. 4A and 4B are graphs of the results for the retention testingdescribed in Example 4.

DETAILED DESCRIPTION Introduction

As discussed above, some conventional antiviral (and/or antimicrobial)polymer compositions, fibers and fabrics utilize antiviral (and/orantimicrobial) compounds to inhibit viruses and other pathogens. Forexample, some fabrics may include antimicrobial additives, e.g., silver,coated or applied as a film on an exterior layer. However, it has beenfound that these treatments or coatings often present a host ofproblems. The inventors have found that, in some conventionalapplications where antiviral additives are components of the fiber, theantiviral additives may extract out of the fibers/fabric during thedyeing process, which adversely affects the antiviral properties of thefiber and detrimentally places the additives into the environment. Inaddition to this problem, the inventors have discovered that someantiviral additives may negatively impact the relative viscosity of theresultant polymer composition.

Some references, e.g., carpet fiber-related references, have disclosedthe use of an antimicrobial nylon prepared in water with a zinc compoundand phosphorus compound to form the carpet fibers. These references,however, relate to higher denier levels (for example, greater than 12dpf) and/or higher fiber diameter (for example, greater than 20 microns)fibers/filaments. These teachings, however are typically not relevant toother types of fibers, e.g., those used in next-to-skin textiles, woventextiles, knitted textiles, filters, masks, or other medical devices.Carpet fibers are formed via entirely different, non-analogous processesequipment, which results in entirely different products. In view ofthese significant differences, the teachings of such carpet fiberreferences are not typically considered relevant to other types offibers/filaments. More specifically, in carpet fiber production,formulations having different amounts, e.g., higher amounts, ofphosphorus compounds (optionally with zinc compounds) are employed fortheir ability to increase relative viscosity of the polymer. However,phosphorous compounds are not typically used in other small fiberpolymer formulations because the use and the accompanying relativeviscosity build might contribute to processability issues. Statedanother way, the equipment and processes cannot process the carpetformulation (with the increased relative viscosity), because it couldimpede processability and make production difficult if not impossible.In contrast to carpet formulations, the polyamide compositions disclosedherein comprise a unique combination of zinc and/or copper andoptionally phosphorus, each preferably in particular amounts, e.g.,lower amounts, that retards or eliminates the viscosity build that isassociated with conventional carpet fiber formulations (and alsoprovides additional synergistic benefits). As a result, the formulationsdisclosed herein are surprisingly capable of forming much thinnerfibers, e.g., in the form of fibers, yarns, or fabric webs, havingantiviral properties, while avoiding the aforementioned processingproblems.

Also, although some references directly mix antiviral and/orantimicrobial agents with fibers, leathers, or plastics, such processesdo not address/solve problems of deterioration of the antiviralproperties of the products, e.g., via extraction loss. Still otherconventional antiviral fabrics have been found to have insufficientstrength for apparel applications, e.g., an inability to withstandsignificant washing, and are unable to retain antimicrobial propertiesover the product lifetime.

It has now been discovered that an effective amount of one or more metalions, preferably zinc and/or copper ions, provides for efficacy fordeactivating virus when incorporated within a hygroscopic polymer. Thesehygroscopic polymers are made into filament yarns and woven or knittedinto textiles. The textiles are made into different articles, such asclothing pieces, medical gowns, medical masks, medical drapes, patienttransfer slip sheets, curtains, bedding (e.g., bedsheets, a duvet, aduvet cover, a pillow, or a pillow cover), luggage (e.g., a suitcase ora garment bag), or footwear (e.g., a shoe upper, a shoe lining, orsewing thread for a shoe).

The use of hygroscopic polymers having ions incorporated thereinprovides a robust and durable fiber/filament yarn that allows thetextile to retain its antiviral efficacy. And the textiles may befinished or dyed and still retain antiviral efficacy. As a result, asynergistic combination of ions incorporated into the hygroscopicpolymer, antiviral efficacy, and retention of each is surprisinglyachieved.

In some embodiments, the use of the phosphorus compound in the specificamounts may allow the metal ions, preferably zinc and/or copper ions tobe more stably disposed in the polymer matrix and, as such, may retardleaching of the zinc/copper compound from the fibers/yarns/fabrics,e.g., during washing and/or dyeing. Stated another way, the polymercomposition may have certain amounts of a zinc/copper compound and aphosphorus compound embedded in the polymer matrix such that the polymercomposition maintains a higher relative viscosity and retainsantimicrobial properties during and after dyeing. In addition, the useof an optional phosphorus compound in the specific amounts may work withthe zinc/copper to improve the relative viscosity of the polymer matrix.

As a result, the disclosed filament yarn made from the hygroscopicpolymer advantageously eliminate the need for a topical antiviraltreatments to the textile. This provides a “built-in” antiviralproperties. And these antiviral properties beneficially will not extractout, e.g., wash away, after dyeing or repeated use. This allows thefilament yarns to be biocompatible and generally regarded as non-toxic.The term “biocompatible” means compatible with living tissue and notproducing toxic, injurious or immunological when exposed to livingtissue.

In addition, the disclosed polymer compositions are able to maintaindesired relative viscosity levels, which provides for advantageousprocessing benefits. Further, the antiviral fibers (or other antiviralproduct) can maintain colorfastness (a characteristic that relates to amaterial's resistance to color fading or running) and durability. Unlikeconventional antiviral fabrics, the present fibers and fabricssubstantially retain their antiviral activity from leaching andextraction during and after dyeing. Further, the present fibers havesignificantly lower denier and lower average diameter, whichbeneficially makes them useful in many end applications, e.g., appareland filtration, where the thicker, higher denier fibers are unsuitable.

Thus, it has now been found that particular substrates, e.g.,polyamides, are able to contain and retain the antiviral/antimicrobialagents and that have high levels of hydrophilicity and/or hygroscopy,present the synergistic ability to attract such liquid media and to thenreduce or inhibit the growth, generally referred to as deactivation, ofthe viruses, as well as microbials that are contained therein.

In addition, as a result of the formulations disclosed herein, thedisclosed polymer compositions, fibers, and/or fabrics do not need to be(and are not) gelled, which adds complications to processing, e.g.,compositional requirements to achieve the gelling and/or processrequirements to do the same, as well as the inability to achieve highthroughput. Thus, the disclosed polymers, fibers, and/or fabrics providethe additional advantages of not including components necessary forgelling as well as elimination of production steps related to thegelling process.

The present disclosure relates to a polymer composition, which may insome cases be used to form antiviral fibers, as well as yarns, and/orfabrics formed therefrom. The polymer composition comprises antiviralagents, which are efficacious and provide for significant resistance toextraction from the fiber. The polymer composition comprises a polymer,zinc ions (provided to the composition via in a zinc compound), and/orcopper ions (provided to the composition via a copper compound) andoptionally phosphorus (provided to the composition via a phosphoruscompound). The polymer may be present in an amount ranging from 50 wt. %to 99.9 wt. %; the zinc/copper ions may be present in an amount rangingfrom 10 wppm to 20,000 wppm, e.g., preferably from 200 to 1000 wppm; andthe phosphorus may be present in an amount less than 1 wt. %. Thepolymer composition may be used to form fibers, and, in addition toimproved antiviral performance, the fibers demonstrate superiorzinc/copper extraction rates, e.g., less than 35% zinc/copper extracted,when tested in a dye bath test (as described herein). The fibers maydemonstrate superior zinc/copper retention rates.

In some embodiments, specific molar ratios of phosphorus to zinc and/orcopper ions are employed, e.g., wherein the phosphorus to zinc and/orcopper molar ratio is at least 0.01:1. Without being bound by theory, bymaintaining a particular phosphorus to zinc and/or copper balance, thepolymer surprisingly achieves desirable relative viscosity levels, e.g.,at least 10, while still maintaining the aforementioned antiviralproperties.

The disclosure also relates to a process for making antiviral fibers (orother antiviral product). The process comprises the steps of providingthe polymer composition having antiviral properties, and forming thepolymer composition into fibers and into filament yarns for textileproduction by woven or knitting methods. It was also beneficially foundthat providing zinc (via a zinc compound) and/or copper (provided to thecomposition via a copper compound) and optionally phosphorus (via aphosphorus compound) to the polymer composition during the productionprocess of the fibers, e.g., to the aqueous monomer solution, producesfibers with antiviral agents evenly dispersed throughout the entirefiber. In conventional processes, a silver coating is applied to theouter surface of the fabric to impart antiviral properties to thefabric. However, the silver coating is not dispersed throughout thefabric and is more susceptible to leaching components, e.g., silver,into the environment. Advantageously, the present polymer compositiondoes not give rise to toxicity because it does not elute the antiviralagents, nor does it include any toxic components, e.g., silver.Additionally, antiviral fibers (or other antiviral product) formed thepresent polymer composition do not require a separate application stepsince the antiviral agents are permanently bound to the polymer matrix.

Hygroscopic Polymers

In one embodiment the filament yarn comprises hygroscopic polymers. Thetextile product may comprises greater than 20% of filament yarnscomprising hygroscopic polymers, e.g., greater than 30%, greater than50%, greater than 75%, greater than 90%, or greater than 99%. In certainembodiments, all the filament yarns that are woven or knitted into thetextile may comprise hygroscopic polymers. As used herein, the term“hygroscopic” refers to polymers that absorb moisture and includeshydrophilic polymers. The inventors have found that the ability toabsorb moisture improves the antiviral efficacy of the metal ions byretaining the virus within the textile to allow for deactivation. Inparticular, the filament yarn made from hygroscopic polymers absorbsand/or attracts liquid media that carry viruses and/or microbials, e.g.,saliva or mucous. The employment of the disclosedantimicrobial/antiviral agents in such substrates, e.g., in the polymermatrices thereof, can be used to more effectively combat the virusesand/or microbials, versus a less hydrophilic substrate.

The hygroscopic polymers surprisingly may benefit from having increasedmoisture absorption. In addition, the inventors have found that certainhydrophilic substrates may better attract liquid media that carryviruses and/or microbials, e.g., saliva or mucous. Also, it is theorizedthat a polymer of increased hydrophilicity and/or hygroscopy both maybetter attract liquid media that carry microbials and/or viruses, e.g.,saliva or mucous, and may also absorb more moisture, e.g., from the air,and that the increased moisture content allows the polymer compositionand the antiviral/antimicrobial agent to more readily limit, reduce, orinhibit infection and/or pathogenesis of a virus. For example, themoisture may dissolve an outer layer, e.g., capsid, of a virus, exposingthe genetic material, e.g., DNA or RNA, of the virus. The exposedgenetic material is more susceptible to deactivation by other componentsof the polymer composition, e.g., the zinc compound, phosphoruscompound, and/or copper compound.

In some cases, the hygroscopic polymers used herein absorbs more than0.3% of moisture based on the weight of the polymer (dry). In preferredembodiments, the hygroscopic polymers used herein is capable ofabsorbing more than 0.5%, e.g. more than 1%, more than 2%, more than 3%,more than 4%, more than 5%, more than 6%, or more than 7%. In contrasthydrophobic polymers, in particular polyolefins, polystyrene, polyvinylchloride and polyphenylsulfone, have lower absorption and poor viralefficacy. Using a natural or synthetic material that absorbs too muchmoisture should be avoided so that virus are not held within thetextile. Thus, suitable ranges for moisture absorption based on theweight of the polymer may be from 0.3% to 10%, including subranges, suchas preferred ranges from 0.3% to 7% or from 0.5% to 5%. These rangesprovide for moisture absorption dimensional stability. The hygroscopy ofa polymer may be measured by saturation.

Hygroscopic polymers as embodied by this disclosure includethermoplastic polymers that include but are not limited to, polyamide,polyurethane, polycarbonate, polyesters, polyacrylates, or acrylonitrilebutadiene styrene. It is envisioned that the filament yarns may be madeof a combination of different hygroscopic polymers. It is preferred thatat least 50% of the filament yarns are made of a polyamide, e.g., atleast 60%, at least 75% or at least 90%. In one embodiment, the filamentyarns do not contain natural fibers, such as cotton, hemp and/or wool.

Suitable polyesters include polyethylene terephthalate (PET) andpolybutylene terephthalate (PBT). The polyesters may be blended withanother hygroscopic polymer. In some embodiments, there may be a blendof polycarbonate and polybutylene terephthalate (PC-PBT) or a blend ofpolycarbonate and polyethylene terephthalate (PC-PET).

Polyamide is a particularly advantageous hygroscopic polymers to be usedfor filament yarn for textile production. Polyamides produce a strongfiber that is thermal stable up to 300° C. exhibits a non-drip burningcharacteristic that is beneficial e.g., in military or automotivetextile applications. The polyamide may be the reaction product, e.g.from polycondensation, of at least one C₄ to C₁₆ aliphatic dicarboxylicacid, cycloaliphatic dicarboxylic acid or aromatic dicarboxylic acidsuch as terephthalic acid and at least one alkylene diamine having from2 to 16 carbon atoms, cycloaliphatic diamine or an aromatic diamine. Thealiphatic monomers may be linear or branched, with linear aliphaticmonomers being preferred. The mass ratio of the dicarboxylic acid todiamine is from 60/40 to 90/10, with equimolar ratios being preferred.In one embodiment, the polyamide may be a reaction product of adipicacid and hexamethylenediamine. In other embodiments, polyamides beproduced through the ring-opening polymerization of lactams, such aspolyamides produced from propriolactam, butyrolactam, valerolactam, andcaprolactam. For example, in some embodiments, the polyamide is apolymer derived from the polymerization of caprolactam. In thoseembodiments, the polymer comprises at least 10 wt. % caprolactam, e.g.,at least 15 wt. %, at least 20 wt. %, at least 25 wt. %, at least 30 wt.%, at least 35 wt. %, at least 40 wt. %, at least 45 wt. %, at least 50wt. %, at least 55 wt. %, or at least 60 wt. %. In some embodiments, thepolymer includes from 10 wt. % to 60 wt. % of caprolactam, e.g., from 15wt. % to 55 wt. %, from 20 wt. % to 50 wt. %, from 25 wt. % to 45 wt. %,or from 30 wt. % to 40 wt. %. In some embodiments, the polymer comprisesless than 60 wt. % caprolactam, e.g., less than 55 wt. %, less than 50wt. %, less than 45 wt. %, less than 40 wt. %, less than 35 wt. %, lessthan 30 wt. %, less than 25 wt. %, less than 20 wt. %, or less than 15wt. %. Furthermore, the polymer composition may comprise the polyamidesproduced through the copolymerization of a lactam, for example, theproduct of the copolymerization of a caprolactam with PA-6,6.

In some cases, the polyamide the polyamide may comprise PA-4T/4I;PA-4T/6I; PA-5T/5I; PA-6; PA-6,6; PA-6,6/6; long chain polyamide (suchas PA-10; PA-12; PA-6,10; PA-6,12, as well as other known long chainvariants optionally including aromatic components, e.g., T and Icomponents); PA-6,6/6T; PA-6T/6I; PA-6T/6I/6; PA-6T/6; PA-6T/6I/66;PA-6T/MPMDT (where MPMDT is polyamide based on a mixture ofhexamethylene diamine and 2-methylpentamethylene diamine as the diaminecomponent and terephthalic acid as the diacid component); PA-6T/66;PA-6T/610; PA-10T/612; PA-10T/106; PA-6T/612; PA-6T/10T; PA-6T/10I;PA-9T; PA-10T; PA-12T; PA-10T/10I; PA-10T/12; PA-10T/1I; PA-6T/9T;PA-6T/12T; PA-6T/10T/6I; PA-6T/6I/6; PA-6T/6I/12; and copolymers,blends, mixtures and/or other combinations thereof. The polymercomposition may, in some embodiments, comprise a combination ofpolyamides. By combining various polyamides, the final composition maybe able to incorporate the desirable properties, e.g., mechanicalproperties, of each constituent polyamides. For example, in someembodiments, the polyamide comprises a combination of PA-6, PA-6,6, andPA-6,6/6T. In these embodiments, the polyamide may comprise from 1 wt. %to 99 wt. % PA-6, from 30 wt. % to 99 wt. % PA-6,6, and from 1 wt. % to99 wt. % PA-6,6/6T. In some embodiments, the polyamide comprises one ormore of PA-6, PA-6,6, and PA-6,6/6T. In some aspects, the polymercomposition comprises 6 wt. % of PA-6 and 94 wt. % of PA-6,6. In someaspects, the polymer composition comprises copolymers or blends of anyof the polyamides mentioned herein. It is preferred at least 50% thefilament yarns are made of PA-6,6, e.g., at least 60%, at least 75% orat least 90%.

In general, filament yarns comprise a hygroscopic polymer in an amountranging from 50 wt. % to 100 wt. %, e.g., from 50 wt. % to 99.99 wt. %,from 50 wt. % to 99.9 wt. %, from 50 wt. % to 99 wt. % from 55 wt. % to100 wt. %, from 55 wt. % to 99.99 wt. %, from 55 wt. % to 99.9 wt. %,from 55 wt. % to 99 wt. %, from 60 wt. % to 100 wt. %, from 60 wt. % to99.99 wt. %, from 60 wt. % to 99.9 wt. %, from 60 wt. % to 99 wt. %.,from 65 wt. % to 100 wt. %, from 65 wt. % to 99.99 wt. %, from 65 wt. %to 99.9 wt. %, or from 65 wt. % to 99 wt. %. In terms of upper limits,the polymer composition may comprise less than 100 wt. % of the polymer,e.g., less than 99.99 wt. %, less than 99.9 wt. %, or less than 99 wt.%. In terms of lower limits, the polymer composition may comprisegreater than 50 wt. % of the polymer, e.g., greater than 55 wt. %,greater than 60 wt. %, or greater than 65 wt. %. In some cases, thecomposition comprises metal ions, preferably zinc and other additives,as discussed herein, and the balance polymer.

Some polymer compositions described herein surprisingly may benefit fromincreased hygroscopy. An increase in hygroscopy may be achieved in theselection and/or modification the polymer. In some embodiments, thepolymer may be a hygroscopic polymer described above, in particularpolyamide, which has been modified to increase hygroscopy. In theseembodiments, a functional endgroup modification on the polymer mayincrease hygroscopy. For example, the polymer may be PA-6,6, which hasbeen modified to include a functional endgroup that increases moistureabsorption within a desired range.

The inventors have found that the content of amine end groups (AEG) mayhave a surprising effect on the performance of the polymer compositions,fibers, and fabrics. As one example, the AEGs have been found to improvethe ability to dye fibers and/or fabrics. The polymer composition mayhave an AEG content ranging from 1 μeq/gram to 105 μeq/gram, e.g., from1 μeq/gram to 75 μeq/gram, from 1 μeq/gram to 55 μeq/gram, from 5μeq/gram to 50 μeq/gram, or from 15 μeq/gram to 40 μeq/gram. In terms ofupper limits, the polymer composition may have an AEG content less than105 μeq/gram, e.g., less than 100 μeq/gram, less than 90 μeq/gram, lessthan 75 μeq/gram, less than 55 μeq/gram, less than 50 μeq/gram, lessthan 45 μeq/gram, less than 40 μeq/gram, less than 35 μeq/gram, lessthan 30 μeq/gram, or less than 25 μeq/gram. In terms of lower limits,the polymer composition may have an AEG content greater than 1 μeq/gram,e.g., greater than 5 μeq/gram, greater than 10 μeq/gram, greater than 15μeq/gram, greater than 20 μeq/gram, greater than 25 μeq/gram, greaterthan 35 μeq/gram, greater than 40 μeq/gram, or greater than 50 μeq/gram.

In some aspects, the polyamide can formed by polymerization condensingof an aqueous solution of at least one diamine-carboxylic acid salt isheated to remove water. This aqueous solution is preferably a mixturewhich includes at least one polyamide-forming salt in combination withmetal compound, such as a zinc, copper, or silver compound. Oncepolymerized is completed the ionization of the metal compounds occursand the polyamide contains metal ions. The absorption of certainmoisture levels promotes the ionization. Thus, the embodiments of thepresent invention incorporate the metal ions into the hygroscopicpolymer, preferably during polymerization and are not later added by atopical treatment.

Metal Ions

As noted above, the filament yarns to produce the textile comprise metalions, preferably divalent metal ions. The metal ions are selected basedas its antiviral efficacy as well as its biocompatibility. It istheorized that the metal ions disrupts the replicative cycle of thevirus. For example, the zinc ions may interfere with (e.g., inhibit)viral protease or polymerase activity. Further discussion of the effectof zinc ions on viral activity is found in Velthuis et al., Zn InhibitsCoronavirus and Arterivirus RNA Polymerase Activity In Vitro and ZincIonophores Block the Replication of These Viruses in Cell Culture, PLoSPathogens (November 2010), which is incorporated herein by reference.Suitable metal ions include but are not limited to zinc, copper, silverand combinations thereof. In one embodiment, it is preferred that atleast 50% of the metal ions are zinc ions, e.g., at least 60%, at least75%, at least 85% or at least 95%.

The metals ions are used in an effective amount to deactivate the virus.An effective amount as used herein referred to an amount of the metalions that when incorporated with the hygroscopic polymer provides anantiviral activity to reduce, prevent growth or eliminate (collectedreferred to as deactivating) the virus exposed to the article. In oneembodiment, an effective amount is enough not to cause clinical symptomson tissue or to reduce transmission rates of the virus. Theconcentration of the metal ions may be greater than or equal to 200wppm, e.g., greater than or equal to 250 wppm, greater than or equal to300 wppm, greater than or equal to 350 wppm, greater than or equal to400 wppm, or greater than or equal to 450 wppm. Lower amounts of metalions tend to have limited efficacy to deactivate virus. Although higheramounts of metals ions may be used it is generally preferred to use aneffective amount in fabric applications. Thus, the ranges of ions may befrom 200 wppm to 1,000 wppm, including subranges therein, such aspreferred ranges from 250 to 950 wppm, from 250 to 800 wppm or 300 to550 wppm, or from 300 to 500 wppm. In some aspects, metal ions areembedded in the polymer.

The metal ions may be incorporated into the hygroscopic polymer duringpolymerization using suitable compounds, such as oxides, carbonates,stearates, pyrithiones, or adipates. This may achieve a widedistribution of the metal ions so that the textile produced by thefilament yarns maintain its antiviral characteristics. In someembodiments, the metal ions are distributed evenly. Once incorporated,the compounds are readily ionized and remain in the ionized form. Thisprovides a filament yarn where the concentration of the one or moremetal ions exceeds the concentration of one or more metal compounds.Thus any loss due to retention is generally of the ions and not themetal compounds. In some embodiments, the one or more metal compoundsincorporated in the hygroscopic polymer is less than 100 wppm, e.g.,less than 50 wppm, less than 25 wppm, less than 10 wppm or less than 5wppm.

In some embodiments, zinc ions (Zn²⁺) are preferred metal ions. The zincions may be provided by one or more zinc oxide, zinc ammonium adipate,zinc acetate, zinc ammonium carbonate, zinc stearate, zinc phenylphosphinic acid, or zinc pyrithione, or combinations thereof. In someaspects, the zinc is provided in the form of zinc oxide. In someaspects, the zinc is not provided via zinc phenyl phosphinate and/orzinc phenyl phosphonate. In some aspects, the zinc compound is ionizedand the zinc ion is embedded in the polymer. The concentration of thezinc ions may be greater than or equal to 200 wppm, e.g., greater thanor equal to 250 wppm, greater than or equal to 300 wppm, greater than orequal to 350 wppm, greater than or equal to 400 wppm, or greater than orequal to 450 wppm. Particularly suitable ranges of zinc ions may be from200 wppm to 1,000 wppm, including subranges therein, such as preferredranges from 250 to 950 wppm, from 250 to 800 wppm or 300 to 550 wppm, orfrom 300 to 500 wppm.

In some cases, the use of zinc provides for processing and or end usebenefits. Other antiviral agents, e.g., copper or silver, may be used,but these often include adverse effects (e.g., on the relative viscosityof the polymer composition, toxicity, and health or environmental risk).In some situations, the zinc compound and zinc ion do not have adverseeffects on the relative viscosity of the polymer composition. Also, thezinc does not present toxicity issues, unlike other antiviral agents,e.g., silver. The use of zinc in some application may provide for healthadvantages, such as immune system support. In addition, as noted herein,the use of zinc ions provides for the reduction or elimination ofleaching into other media and/or into the environment. This bothprevents the risks associated with introducing zinc into the environmentand allows the polymer composition to be reused—zinc provides surprising“green” advantages over other types of antivirals, e.g.,silver-containing, compositions.

As noted above, copper ions (provided via a copper compound) may beincorporated into the hygroscopic polymers. The copper ions may be usedindependently or in combination with zinc ions. In some cases, thecopper compound may improve, e.g., enhance the antiviral properties ofthe polymer composition. In some cases, the copper compound may affectother characteristics of the polymer composition, e.g., antimicrobialactivity or physical characteristics.

When used independently, the concentration of the copper ions may begreater than or equal to 200 wppm, e.g., greater than or equal to 250wppm, greater than or equal to 300 wppm, greater than or equal to 350wppm, greater than or equal to 400 wppm, or greater than or equal to 450wppm. Particularly suitable ranges of copper ions may be from 200 wppmto 1,000 wppm, including subranges therein, such as preferred rangesfrom 250 to 950 wppm, from 250 to 800 wppm or 300 to 550 wppm, or from300 to 500 wppm.

When copper ions are used as a promoter with zinc ions, theconcentration of copper ions may be lower. In one embodiment, the molarratio of the copper ions to the zinc ions is greater than 0.01:1, e.g.,greater than 0.05:1, greater than 0.1:1, greater than 0.15:1, greaterthan 0.25:1, greater than 0.5:1, or greater than 0.75:1. In terms ofranges, the molar ratio of the copper ions to the zinc ions in thehygroscopic polymer may range from 0.01:1 to 15:1, e.g., from 0.05:1 to10:1, from 0.1:1 to 9:1, from 0.15:1 to 8:1, from 0.25:1 to 7:1, from0.5:1 to 6:1, from 0.75:1 to 5:1 from 0.5:1 to 4:1, or from 0.5:1 to3:1. In terms of upper limits, the molar ratio of zinc ions to copperions in the hygroscopic polymer may be less than 15:1, e.g., less than10:1, less than 9:1, less than 8:1, less than 7:1, less than 6:1, lessthan 5:1, less than 4:1, or less than 3:1. In some cases, copper ion isbound to hygroscopic polymer along with zinc ion.

In some embodiments, copper ions as a promoter may be present in amountsgreater than or equal to 5 wppm when used with zinc ions in an amountgreater than or equal to 200 wppm. More preferably, copper ions as apromoter with zinc ions, may be present in amounts greater than or equalto 10 wppm, greater than or equal to 15 wppm, greater than or equal to20 wppm, greater than or equal to 25 wppm, greater than or equal to 50wppm, greater than or equal to 100 wppm. In one embodiment, thehygroscopic polymers comprises copper ions as a promoter in an amountranging from 5 wppm to 800 wppm, e.g., from 10 wppm to 750 wppm, from 10wppm to 600 wppm, from 10 wppm to 500 wppm, from 10 wppm to 400 wppm,from 10 wppm to 300 wppm, from 10 wppm to 250 wppm, from 10 wppm to 200wppm, or from 10 wppm to 150 wppm.

The composition of the copper compound is not particularly limited.Suitable copper compounds include copper iodide, copper bromide, copperchloride, copper fluoride, copper oxide, copper stearate, copperammonium adipate, copper acetate, or copper pyrithione, or combinationsthereof. The copper compound may comprise copper oxide, copper ammoniumadipate, copper acetate, copper ammonium carbonate, copper stearate,copper phenyl phosphinic acid, or copper pyrithione, or combinationsthereof. In some embodiments, the copper compound comprises copperoxide, copper ammonium adipate, copper acetate, or copper pyrithione, orcombinations thereof. In some embodiments, the copper compound comprisescopper oxide, copper stearate, or copper ammonium adipate, orcombinations thereof. In some aspects, the copper is provided in theform of copper oxide. In some aspects, the copper is not provided viacopper phenyl phosphinate and/or copper phenyl phosphonate.

As noted above, silver ions (provided via a silver compound) may beincorporated into the hygroscopic polymers. The silver ions may be usedindependently or in combination with zinc ions and/or copper ions. Insome cases, the silver compound may improve, e.g., enhance the antiviralproperties of the polymer composition. In some cases, the silvercompound may affect other characteristics of the polymer composition,e.g., antimicrobial activity or physical characteristics.

When used independently, the concentration of the silver ions may begreater than or equal to 200 wppm, e.g., greater than or equal to 250wppm, greater than or equal to 300 wppm, greater than or equal to 350wppm, greater than or equal to 400 wppm, or greater than or equal to 450wppm. Particularly suitable ranges of silver ions may be from 200 wppmto 1,000 wppm, including subranges therein, such as preferred rangesfrom 250 to 950 wppm, from 250 to 800 wppm or 300 to 550 wppm, or from300 to 500 wppm.

When silver ions are used as a promoter with zinc and/or copper ions,the concentration of silver ions may be lower. In one embodiment, themolar ratio of the silver ions to the zinc ions and/or copper ions isgreater than 0.01:1, e.g., greater than 0.05:1, greater than 0.1:1,greater than 0.15:1, greater than 0.25:1, greater than 0.5:1, or greaterthan 0.75:1. In terms of ranges, the molar ratio of the silver ions tothe zinc ions and/or copper ions in the hygroscopic polymer may rangefrom 0.01:1 to 15:1, e.g., from 0.05:1 to 10:1, from 0.1:1 to 9:1, from0.15:1 to 8:1, from 0.25:1 to 7:1, from 0.5:1 to 6:1, from 0.75:1 to 5:1from 0.5:1 to 4:1, or from 0.5:1 to 3:1. In terms of upper limits, themolar ratio of zinc ions and/or copper ions to silver ions in thehygroscopic polymer may be less than 15:1, e.g., less than 10:1, lessthan 9:1, less than 8:1, less than 7:1, less than 6:1, less than 5:1,less than 4:1, or less than 3:1. In some cases, silver ion is bound tohygroscopic polymer along with zinc ion and/or copper ions.

In some embodiments, silver ions as a promoter may be present in amountsgreater than or equal to 5 wppm when used with zinc ions in an amountgreater than or equal to 200 wppm. More preferably, silver ions as apromoter with zinc ions, may be present in amounts greater than or equalto 10 wppm, greater than or equal to 15 wppm, greater than or equal to20 wppm, greater than or equal to 25 wppm, greater than or equal to 50wppm, greater than or equal to 100 wppm. In one embodiment, thehygroscopic polymers comprises silver ions as a promoter in an amountranging from 5 wppm to 800 wppm, e.g., from 10 wppm to 750 wppm, from 10wppm to 600 wppm, from 10 wppm to 500 wppm, from 10 wppm to 400 wppm,from 10 wppm to 300 wppm, from 10 wppm to 250 wppm, from 10 wppm to 200wppm, or from 10 wppm to 150 wppm.

The composition of the silver compound is not particularly limited.Suitable silver compounds include silver iodide, silver bromide, silverchloride, silver fluoride, silver oxide, silver stearate, silverammonium adipate, silver acetate, or silver pyrithione, or combinationsthereof. The silver compound may comprise silver oxide, silver ammoniumadipate, silver acetate, silver ammonium carbonate, silver stearate,silver phenyl phosphinic acid, or silver pyrithione, or combinationsthereof. In some embodiments, the silver compound comprises silveroxide, silver ammonium adipate, silver acetate, or silver pyrithione, orcombinations thereof. In some embodiments, the silver compound comprisessilver oxide, silver stearate, or silver ammonium adipate, orcombinations thereof. In some aspects, the silver is provided in theform of silver oxide. In some aspects, the silver is not provided viasilver phenyl phosphinate and/or silver phenyl phosphonate.

The hygroscopic polymer may comprise phosphorus (in a phosphoruscompound), e.g., phosphorus or a phosphorus compound is dispersedtherein with the metal ions. In one embodiment, the polymer compositioncomprises phosphorus in an amount ranging from 50 wppm to 10000 wppm,e.g., from 50 wppm to 5000 wppm, from 50 wppm to 2500 wppm, from 50 wppmto 2000 wppm, from 50 wppm to 800 wppm, 100 wppm to 750 wppm, 100 wppmto 1800 wppm, from 100 wppm to 10000 wppm, from 100 wppm to 5000 wppm,from 100 wppm to 2500 wppm, from 100 wppm to 1000 wppm, from 100 wppm to800 wppm, from 200 wppm to 10000 wppm, 200 wppm to 5000 wppm, from 200wppm to 2500 wppm, from 200 ppm to 800 wppm, from 300 wppm to 10000wppm, from 300 wppm to 5000 wppm, from 300 wppm to 2500 wppm, from 300wppm to 500 wppm, from 500 wppm to 10000 wppm, from 500 wppm to 5000wppm, or from 500 wppm to 2500 wppm. In terms of lower limits, thepolymer composition may comprise greater than or equal to 50 wppm ofphosphorus, e.g., greater than or equal to 75 wppm, greater than orequal to 100 wppm, greater than or equal to 150 wppm, greater than orequal to 200 wppm, greater than or equal to 300 wppm or greater than orequal to 500 wppm. In terms of upper limits, the polymer composition maycomprise less than 10000 wppm (or 1 wt. %), e.g., less than 5000 wppm,less than 2500 wppm, less than 2000 wppm, less than 1800 wppm, less than1500 wppm, less than 1000 wppm, less than 800 wppm, less than 750 wppm,less than 500 wppm, less than 475 wppm, less than 450 wppm, or less than400 wppm. In some aspects, the phosphorus or the phosphorus compound isembedded in the polymer formed from the polymer composition.

The phosphorus optionally is present in or provided via a phosphoruscompound, which may vary widely. The phosphorus compound may comprisebenzene phosphinic acid, diphenylphosphinic acid, sodiumphenylphosphinate, phosphorous acid, benzene phosphonic acid, calciumphenylphosphinate, potassium B-pentylphosphinate, methylphosphinic acid,manganese hypophosphite, sodium hypophosphite, monosodium phosphate,hypophosphorous acid, dimethylphosphinic acid, ethylphosphinic acid,diethylphosphinic acid, magnesium ethylphosphinate, triphenyl phosphite,diphenylrnethyl phosphite, dimethylphenyl phosphite, ethyldiphenylphosphite, phenylphosphonic acid, methylphosphonic acid, ethylphosphonicacid, potassium phenylphosphonate, sodium methylphosphonate, calciumethylphosphonate, and combinations thereof. In some embodiments, thephosphorus compound comprises phosphoric acid, benzene phosphinic acid,or benzene phosphonic acid, or combinations thereof. In someembodiments, the phosphorus compound comprises benzene phosphinic acid,phosphorous acid, or manganese hypophosphite, or combinations thereof.In some aspects, the phosphorus compound may comprise benzene phosphinicacid.

In one embodiment, the molar ratio of the phosphorus to the zinc ions isgreater than 0.01:1, e.g., greater than 0.05:1, greater than 0.1:1,greater than 0.15:1, greater than 0.25:1, greater than 0.5:1, or greaterthan 0.75:1. In terms of ranges, the molar ratio of the phosphorus tothe zinc ions in the polymer composition may range from 0.01:1 to 15:1,e.g., from 0.05:1 to 10:1, from 0.1:1 to 9:1, from 0.15:1 to 8:1, from0.25:1 to 7:1, from 0.5:1 to 6:1, from 0.75:1 to 5:1 from 0.5:1 to 4:1,or from 0.5:1 to 3:1. In terms of upper limits, the molar ratio of zincions to phosphorus in the polymer composition may be less than 15:1,e.g., less than 10:1, less than 9:1, less than 8:1, less than 7:1, lessthan 6:1, less than 5:1, less than 4:1, or less than 3:1. In some cases,phosphorus is bound in the polymer matrix along with zinc ions or otherions.

In one embodiment, the weight ratio of zinc ions to phosphorus in thepolyamide composition may be greater than 1.3:1, e.g., greater than1.4:1, greater than 1.5:1, greater than 1.6:1, greater than 1.7:1,greater than 1.8:1, or greater than 2:1. In terms of ranges, the weightratio of zinc to phosphorus in the polyamide composition may range from1.3:1 to 30:1, e.g., from 1.4:1 to 25:1, from 1.5:1 to 20:1, from 1.6:1to 15:1, from 1.8:1 to 10:1, from 2:1 to 8:1, from 3:1 to 7:1, or from4:1 to 6:1. In terms of upper limits, the weight ratio of zinc tophosphorus in the polyamide composition may be less than 30:1, e.g.,less than 28:1, less than 26:1, less than 24:1, less than 22:1, lessthan 20:1, or less than 15:1. In some aspects, there is no phosphorus inthe polyamide composition. In other aspects, a very low amount ofphosphorus is present. In some cases, phosphorus is held in the polymermatrix along with zinc.

In one embodiment, the weight ratio of zinc to phosphorus in thepolyamide composition may be less than 0.64:1, e.g., less than 0.62:1,less than 0.6:1, e.g., less than 0.5:1, less than 0.45:1, less than0.4:1, less than 0.3:1, or less than 0.25:1. In terms of ranges, theweight ratio of zinc to phosphorus in the polyamide composition mayrange from 0.001:1 to 0.64:1, e.g., from 0.01:1 to 0.6:1, from 0.05:1 to0.5:1, from 0.1:1 to 0.45:1, from 0.2:1 to 0.4:1, from 0.25:1 to 0.35:1,or from 0.2:1 to 0.3:1. In terms of lower limits, the weight ratio ofzinc to phosphorus in the polyamide composition may be greater than0.001:1, e.g., greater than 0.005:1, greater than 0.01:1, greater than0.05:1, greater than 0.1:1, greater than 0.15:1, or greater than 0.2:1.

Advantageously, it has been discovered that adding the above identifiedzinc compounds and phosphorus compounds may result in a beneficialrelative viscosity of the polymer composition. In some embodiments, therelative viscosity of the polymer composition ranges from 10 to 70,e.g., from 15 to 65, from 20 to 60, from 30 to 50, from 10 to 35, orfrom 15 to 32. In terms of lower limits, the relative viscosity of thepolymer composition may be greater than or equal to 10, e.g., greaterthan or equal to 15, greater than or equal to 20, greater than or equalto 25, greater than or equal to 27.5, or greater than or equal to 30. Interms of upper limits, the relative viscosity of the polymer compositionmay be less than 70, e.g., less than 65, less than 60, less than 50,less than 40, or less than 35.

It has been determined that a specific amount of the zinc compound andthe phosphorus compound can be mixed in a polymer composition, e.g.,polyamide composition, in finely divided form, such as in the form ofgranules, flakes and the like, to provide a polymer composition that canbe subsequently formed, e.g., extruded, molded or otherwise drawn, intovarious products (e.g., high-contact products, surface layers ofhigh-contact products) by conventional methods to produce productshaving substantially improved antimicrobial activity. The zinc andphosphorus are employed in the polymer composition in the aforementionedamounts to provide a fiber with improved antimicrobial activityretention (near-permanent).

Zinc/Copper Retention Rate

As noted herein, by utilizing a polymer composition having theaforementioned metal ion, preferably zinc ions, and/or optionalphosphorus compound in an effective amount, the resultant textile iscapable of retaining a higher percentage of metal ions, even afterdyeing. The resulting filament yarns and textiles are durable havingnear-permanent antiviral properties. The values associated with theretention rates discussed herein are also applicable to the individualmetal ions.

In some embodiments, the antiviral fibers have a metal ions retentiongreater than or equal to 65% as measured by a dye bath test, e.g.,greater than or equal to 75%, greater than or equal to 80%, greater thanor equal to 90%, greater than or equal to 95%, greater than or equal to97%, greater than or equal to 98%, greater than or equal to 99%, greaterthan or equal to 99.9%, greater than or equal to 99.99%, greater than orequal to 99.999%, greater than or equal to 99.9999%, greater than orequal to 99.99999% or greater than or equal to 99.999999%. In terms ofupper limits, the antiviral fiber has a metal ions of less than 100%,e.g., less than 99.9%, less than 98%, or less than 95%. In terms ofranges, the antiviral fiber has a metal ions may be from 60% to 100%,e.g., from 60% to 99.999999%, from 60% to 99.99999%, from 60% to99.9999%, from 60% to 99.999% from 60% to 99.999%, from 60% to 99.99%,from 60% to 99.9%, from 60% to 99%, from 60% to 98%, from 60% to 95%,from 65% to 99.999999%, from 65% to 99.99999%, from 65% to 99.9999%,from 65% to 99.999% from 65% to 99.999%, from 65% to 100%, from 65% to99.99%, from 65% to 99.9%, from 65% to 99%, from 65% to 98%, from 65% to95%, from 70% to 100%, from 70% to 99.999999%, from 70% to 99.99999%,from 70% to 99.9999%, from 70% to 99.999% from 70% to 99.999%, from 70%to 99.99%, from 70% to 99.9%, from 70% to 99%, from 70% to 98%, from 70%to 95%, from 75% to 100%, from 75% to 99.99%, from 75% to 99.9%, from75% to 99.999999%, from 75% to 99.99999%, from 75% to 99.9999%, from 75%to 99.999% from 75% to 99.999%, from 75% to 99%, from 75% to 98%, from75% to 95%, %, from 80% to 99.999999%, from 80% to 99.99999%, from 80%to 99.9999%, from 80% to 99.999% from 80% to 99.999%, from 80% to 100%,from 80% to 99.99%, from 80% to 99.9%, from 80% to 99%, from 80% to 98%,or from 80% to 95%. In some cases, the ranges and limits relate to dyerecipes having lower pH values, e.g., less than (and/or including) 5.0,less than 4.7, less than 4.6, or less than 4.5. In some cases, theranges and limits relate to dye recipes having higher pH values, e.g.,greater than (and/or including) 4.0, greater than 4.2, greater than 4.5,greater than 4.7, greater than 5.0, or greater than 5.0.

In some embodiments, the antiviral fibers (or other antiviral products)formed from the polymer composition have a metal ions retention greaterthan or equal to 40% after a dye bath, e.g., greater than or equal to44%, greater than or equal to 45%, greater than or equal to 50%, greaterthan or equal to 55%, greater than or equal to 60%, greater than orequal to 65%, greater than or equal to 70%, greater than or equal to75%, greater than or equal to 80%, greater than or equal to 90%, greaterthan or equal to 95%, or greater than or equal to 99%. In terms of upperlimits, the antiviral fibers may have a metal ions retention of lessthan 100%, e.g., less than 99.9%, less than 98%, less than 95% or lessthan 90%. In terms of ranges, the antiviral fiber has a metal ionsretention in a range from 40% to 100%, e.g., from 45% to 99.9%, from 50%to 99.9%, from 75% to 99.9%, from 80% to 99%, or from 90% to 98%. Insome cases, the ranges and limits relate to dye recipes having higher pHvalues, e.g., greater than (and/or including) 4.0, greater than 4.2,greater than 4.5, greater than 4.7, greater than 5.0, or greater than5.0.

In some embodiments, the antiviral fibers (or other antiviral products)formed from the polymer composition have a metal ions retention greaterthan or equal to 20%, e.g., greater than 24%, greater than or equal to25%, greater than or equal to 30%, greater than or equal to 35%, greaterthan or equal to 40%, greater than or equal to 45%, greater than orequal to 50%, greater than or equal to 55%, or greater than or equal to60%. In terms of upper limits, the antiviral fibers may have a metalions of less than 80%, e.g., less than 77%, less than 75%, less than70%, less than 68%, or less than 65%. In terms of ranges, the antiviralfibers may have a zinc and/or copper retention ranging from 20% to 80%,e.g., from 25% to 77%, from 30% to 75%, or from 35% to 70%. In somecases, the ranges and limits relate to dye recipes having lower pHvalues, e.g., less than (and/or including) 5.0, less than 4.7, less than4.6, or less than 4.5.

In some embodiments, the antiviral fibers (or other antiviral products)formed from the polymer composition demonstrate an extraction rate ofthe metal ions less than 35% as measured by the dye bath test, e.g.,less than 25%, less than 20%, less than 10%, or less than 5%. In termsof upper limits, the antiviral fiber demonstrates an extraction rate ofthe metal ions greater than or equal to 0%, e.g., greater than or equalto 0.1%, greater than or equal to 2% or greater than or equal to 5%. Interms of ranges, the antiviral fiber demonstrates an extraction rate ofthe metal ions from 0% to 35%, e.g., from 0% to 25%, from 0% to 20%,from 0% to 10%, from 0% to 5%, from 0.1% to 35%, from 0.1% to 25%, from0.1% to 20%, from 0.2% to 10%, from 0.1% to 5%, from 2% to 35%, from 2%to 25%, from 2% to 20%, from 2% to 10%, from 2% to 5%, from 5% to 35%,from 5% to 25%, from 5% to 20%, or from 5% to 10%.

The metal ions of a fiber (or other product) formed from the polymercomposition may be measured by a dye bath test according to thefollowing standard procedure. A sample is cleaned (all oils are removed)by a scour process. The scour process may employ a heated bath, e.g.,conducted at 71° C. for 15 minutes. A scouring solution comprising 0.25%on weight of fiber (“owf”) of Sterox (723 Soap) nonionic surfactant and0.25% owf of TSP (trisodium phosphate) may be used. The samples werethen rinsed with water and then rinsed with cold water.

The cleaned samples may be tested according a chemical dye levelprocedure. This procedure may employ placing them in a dye bathcomprising 1.0% owf of C.I. Acid Blue 45, 4.0% owf of MSP (monosodiumphosphate), and a sufficient % owf of disodium phosphate or TSP toachieve a pH of 6.0, with a 28:1 liquor to fiber ratio. For example, ifa pH of less than 6 is desired, a 10% solution of the desired acid maybe added using an eye dropper until the desired pH was achieved. The dyebath may be preset to bring the bath to a boil at 100° C. The samplesare placed in the bath for 1.5 hours. As one example, it may takeapproximately 30 minutes to reach boil and hold one hour after boil atthis temperature. Then the samples are removed from the bath and rinsed.The samples are then transferred to a centrifuge for water extraction.After water extraction, the samples were laid out to air dry. Thecomponent amounts are then recorded.

In some embodiments, the metal ions of a fiber formed from the polymercomposition may be calculated by measuring metal ions content before andafter a dye bath operation. The amount of metal ions retained after thedye bath may be measured by known methods. For the dye bath, an Ahibadyer (from Datacolor) may be employed. In a particular instance, twentygrams of un-dyed fabric and 200 ml of dye liquor may be placed in astainless steel can, the pH may be adjusted to the desired level, thestainless steel can may be loaded into the dyer; the sample may beheated to 40° C. then heated to 100° C. (optionally at 1.5° C./minute).In some cases a temperature profile may be employed, for example, 1.5°C./minute to 60° C., 1° C./minute to 80° C., and 1.5° C./minute to 100°C. The sample may be held at 100° C. for 45 minutes, followed by coolingto 40° C. at 2° C./minute, then rinsed and dried to yield the dyedproduct.

In addition to the antimicrobial/antiviral (AM/AV) properties, thedisclosed compositions surprisingly demonstrated improved zinc retentionafter washing (washfastness) of the polymer. The zinc retention may becharacterized in relation to washes. The fiber and/or fabric is capableof retaining a higher percentage of zinc and/or copper, even afterwashing, as such the resulting yarns formed from the fibers have AM/AVproperties.

In some embodiments, the AM/AV fibers formed from the polymercomposition have a zinc and/or copper retention greater than or equal to85% as measured in after 5 washes, e.g., greater than or equal to 90%,greater than or equal to 92%, greater than or equal to 95%, greater thanor equal to 96%, greater than or equal to 98%, greater than or equal to99%, or greater than or equal to 99.9%.

In some embodiments, the AM/AV fibers formed from the polymercomposition have a zinc and/or copper retention greater than or equal to65% as measured in after 10 washes, e.g., greater than or equal to 70%,greater than or equal to 72%, greater than or equal to 80%, greater thanor equal to 85%, greater than or equal to 90%, greater than or equal to95%, greater than or equal to 99%.

Antiviral Activity

The hygroscopic polymers have incorporated therein metal ions describedherein exhibit antiviral properties, e.g., antiviral activity.Furthermore, the filament yarns and textile that are woven or knittedfrom the filament yarns, made of the hygroscopic polymers describedherein exhibit antiviral properties. In particular, by utilizing ahygroscopic polymers having the aforementioned zinc, copper, silverand/or phosphorus compounds in an effective amount an article exhibitingantiviral properties can be prepared.

In some embodiments, the polymer compositions, and the products formedtherefrom, exhibit durable antiviral characteristics that are permanentin nature, e.g., near permanent in nature. The durable antiviralproperties last for a prolonged period of time, e.g., longer than one ormore day, longer than one or more week, longer than one or more month,or longer than one or more years and allow the articles to be reused.

The antiviral properties may include any deactivating effect. In someembodiments, for example, the antiviral properties of the polymercomposition include limiting, reducing, or inhibiting infection of avirus. In some embodiments, the antiviral properties of the polymercomposition include limiting, reducing, or inhibiting pathogenesis of avirus. In some cases, the polymer composition may limit, reduce, orinhibit both infection and pathogenesis of a virus.

The virus affected by the antiviral properties of the polymercomposition is not particularly limited. In some embodiments, forexample, the virus is an adenovirus, a herpesvirus, an ebolavirus, apoxvirus, a rhinovirus, a coxsackievirus, an arterivirus, anenterovirus, a morbillivirus, a coronavirus, an influenza A virus, anavian influenza virus, a swine-origin influenza virus, or an equineinfluence virus. In some embodiments, the antiviral properties includelimiting, reducing, or inhibiting the infection or pathogenesis of oneof virus, e.g., a virus from the above list. In some embodiments, theantiviral properties include limiting, reducing, or inhibiting theinfection or pathogenesis of multiple viruses, e.g., a combination oftwo or more viruses from the above list.

In some cases, the virus is a coronavirus, e.g., severe acuterespiratory syndrome coronavirus (SARS-CoV), Middle East respiratorysyndrome coronavirus (MERS-CoV), or severe acute respiratory syndromecoronavirus 2 (SARS-CoV-2) (e.g., the coronavirus that causes COVID-19).In some cases, the virus is structurally related to a coronavirus.

In some cases, the virus is an influenza virus, such as an influenza Avirus, an influenza B virus, an influenza C virus, or an influenza Dvirus, or a structurally related virus. In some cases, the virus isidentified by an influenza A virus subtype, e.g., H1N1, H1N2, H2N2,H2N3, H3N1, H3N2, H3N8, H5N1, H5N2, H5N3, H5N6, H5N8, H5N9, H6N1, H7N1,H7N4, H7N7, H7N9, H9N2, or H10N7.

In some cases, the virus is a the virus is a bacteriophage, such as alinear or circular single-stranded DNA virus (e.g., phi X 174 (sometimesreferred to as ΦX174)), a linear or circular double-stranded DNA, alinear or circular single-stranded RNA, or a linear or circulardouble-stranded RNA. In some cases, the antiviral properties of thepolymer composition may be measured by testing using a bacteriophage,e.g., phi X 174.

In some cases, the virus is an ebolavirus, e.g., Bundibugyo ebolavirus(BDBV), Reston ebolavirus (RESTV), Sudan ebolavirus (SUDV), Taï Forestebolavirus (TAFV), or Zaire ebolavirus (EBOV). In some cases, the virusis structurally related to an ebolavirus.

The antiviral activity is demonstrated through testing. General thedeactivation is shown by the log reduction. To achieve antiviralefficacy of at least a 2-log reduction (99%) is desirable over a limitedcontact period.

The antiviral activity may be measured by a variety of conventionalmethods. For example, ISO18184:2019 may be utilized to assess theantiviral activity. In one embodiment, the polymer composition, e.g., afiber, yarn, fabric, and/or nonwoven polymer structure formed from thepolymer composition inhibits the pathogenesis (e.g., growth) of a virusin an amount ranging from 60% to 100% (complete kill), e.g., from 60% to99.999999%, from 60% to 99.99999%, from 60% to 99.9999%, from 60% to99.999% from 60% to 99.999%, from 60% to 99.99%, from 60% to 99.9%, from60% to 99%, from 60% to 98%, from 60% to 95%, from 65% to 99.999999%,from 65% to 99.99999%, from 65% to 99.9999%, from 65% to 99.999% from65% to 99.999%, from 65% to 100%, from 65% to 99.99%, from 65% to 99.9%,from 65% to 99%, from 65% to 98%, from 65% to 95%, from 70% to 100%,from 70% to 99.999999%, from 70% to 99.99999%, from 70% to 99.9999%,from 70% to 99.999% from 70% to 99.999%, from 70% to 99.99%, from 70% to99.9%, from 70% to 99%, from 70% to 98%, from 70% to 95%, from 75% to100%, from 75% to 99.99%, from 75% to 99.9%, from 75% to 99.999999%,from 75% to 99.99999%, from 75% to 99.9999%, from 75% to 99.999% from75% to 99.999%, from 75% to 99%, from 75% to 98%, from 75% to 95%, from80% to 99.999999%, from 80% to 99.99999%, from 80% to 99.9999%, from 80%to 99.999% from 80% to 99.999%, from 80% to 100%, from 80% to 99.99%,from 80% to 99.9%, from 80% to 99%, from 80% to 98%, from 80% to 95%, orfrom 90% to 99.999%, 99% to 99.999% or 99% to 99.9%. In terms of lowerlimits, a fiber formed from the polymer composition may inhibit (i.e.deactivate) greater than or equal to 60% of pathogenesis of the virus,e.g., greater than or equal to 65%, greater than or equal to 70%,greater than or equal to 75%, greater than or equal to 80%, greater thanor equal to 85%, greater than or equal to 90%, greater than or equal to95%, greater than or equal to 98%, greater than or equal to 99%, greaterthan or equal to 99.9%, greater than or equal to 99.99%, greater than orequal to 99.999%, greater than or equal to 99.9999%, greater than orequal to 99.99999%, or greater than or equal to 99.999999%.

In some cases, the efficacy may be measured in term of log reduction.For example, the composition/fibers/fabrics may demonstrate a virus logreduction greater than 1.0-log, as determined via ISO 18184 (2019),e.g., greater than 1.5-log, greater than 1.7-log, greater than 1.9-log,greater than 2.0-log, greater than 3.0-log, greater than 4.0-log, orgreater than 5.0-log.

Self-Cleaning/Virus-Inactivating Fabrics

In some cases, the disclosure relates to self-cleaning and/or virus- ormicrobial-inactivating fabrics that may comprise the fabrics andcompositions disclosed herein. In some embodiments, the fabrics areconfigured into masks or other personal protective equipment (PPE). Facemasks and other PPE can reduce risk of spreading or getting infectedwith respiratory viruses, such as SARS-CoV-2, the causative agent ofCovid-19. However, in some instances (where the microbial/virus is notinactivated), the viruses/microbes can remain infectious in or on theoutside of conventional PPE for extended periods of time.

This disclosure relates to self-cleaning and/or virus- ormicrobial-inactivating fabrics that have the synergistic combination ofthe ability to trap the virus/microbe and the ability to inactivate orneutralize the virus/microbe. As such, the disclosed fabrics are able tocapture and inactivate viruses/microbes before they reach the protecteduser. In contrast, hydrophobic polymers, such as polypropylene, areunable to effectively trap the microbial/virus for enough time forinactivation.

It has been discovered that respiratory viruses/microbes can beadvantageously inactivated via absorption of droplet containing theviruses/microbes and inactivation thereof on the surface and within thebulk of the fabric. In some embodiments, the fabrics may be constructedfrom polymers that maintain a moisture balance, e.g., polyamides, andcontain embedded zinc ions within their matrix to inactivate anyrespiratory viruses.

Additional Components

In some embodiments, the polymer composition may comprise additionaladditives for textile and fabric applications. The additives includepigments, hydrophilic or hydrophobic additives, anti-odor additives,additional antiviral agents, and antimicrobial/anti-fungal inorganiccompounds, such as copper, zinc, tin, and silver.

In some embodiments, the polymer composition can be combined with colorpigments for coloration for the use in fabrics or other componentsformed from the polymer composition. In some aspects, the polymercomposition can be combined with UV additives to withstand fading anddegradation in fabrics exposed to significant UV light. In some aspects,the polymer composition can be combined with additives to make thesurface of the fiber hydrophilic or hydrophobic. In some aspects, thepolymer composition can be combined with a hygroscopic material, e.g.,to make the fiber, fabric, or other products formed therefrom morehygroscopic. In some aspects, the polymer composition can be combinedwith additives to make the fabric flame retardant or flame resistant. Insome aspects, the polymer composition can be combined with additives tomake the fabric stain resistant. In some aspects, the polymercomposition can be combined with pigments with the antimicrobialcompounds so that the need for conventional dyeing and disposal of dyematerials is avoided.

In some embodiments, the polymer composition may further compriseadditional additives. For example, the polymer composition may comprisea delusterant. A delusterant additive may improve the appearance and/ortexture of the synthetic fibers and fabric produced from the polymercomposition. In some embodiments, inorganic pigment-like materials canbe utilized as delusterants. The delusterants may comprise one or moreof titanium dioxide, barium sulfate, barium titanate, zinc titanate,magnesium titanate, calcium titanate, zinc oxide, zinc sulfide,lithopone, zirconium dioxide, calcium sulfate, barium sulfate, aluminumoxide, thorium oxide, magnesium oxide, silicon dioxide, talc, mica, andthe like. In preferred embodiments, the delusterant comprises titaniumdioxide. It has been found that the polymer compositions that includedelusterants comprising titanium dioxide produce synthetic fibers andfabrics that greatly resemble natural fibers and fabrics, e.g.,synthetic fibers and fabrics with improved appearance and/or texture. Itis believed that titanium dioxide improves appearance and/or texture byinteracting with the zinc compound, the phosphorus compound, and/orfunctional groups within the polymer.

In one embodiment, the polymer composition comprises the delusterant inan amount ranging from 0.0001 wt. % to 3 wt. %, e.g., 0.0001 wt. % to 2wt. %, from 0.0001 to 1.75 wt. %, from 0.001 wt. % to 3 wt. %, from0.001 wt. % to 2 wt. %, from 0.001 wt. % to 1.75 wt. %, from 0.002 wt. %to 3 wt5, from 0.002 wt. % to 2 w %, from 0.002 wt. % to 1.75 wt. %,from 0.005 wt. % to 3 wt. %, from 0.005 wt. % to 2 wt. %, from 0.005 wt.% to 1.75 wt. %. In terms of upper limits, the polymer composition maycomprise less than 3 wt. % delusterant, e.g., less than 2.5 wt. %, lessthan 2 wt. % or less than 1.75 wt. %. In terms of lower limits, thepolymer composition may comprise greater than 0.0001 wt. % delusterant,e.g., greater than 0.001 wt. %, greater than 0.002 wt. %, or greaterthan 0.005 wt. %.

In some embodiments, the polymer compositions (and the products producedtherefrom) advantageously comprise little or no content of processingaids such as surfactants and/or coupling agents (see discussion above).In some cases, the polymer compositions comprise less than 100 wppmsurfactant and/or coupling agent, e.g., less than 50 wppm, less thanless than 20 wppm, less than 10 wppm, or less than 5 wppm. In terms ofranges, the polymer compositions may comprise from 1 wppb to 100 wppm,e.g., from 1 wppb to 20 wppm, from 1 wppb to 10 wppm, or from 1 wppb to5 wppm. The disclosed compositions may not employ any surfactant and/orcoupling agent at all. There can be no surfactant and/or coupling agentpresent after processing, which is not the case for conventionalformulations that do employ surfactant and/or coupling agents asnecessary components. Even though some of these components may burn offduring processing, some surfactant and/or coupling agent will remain inthe resultant fibers.

Common surfactants include anionic surfactants, cationic surfactantsand/or non-ionic surfactants. Specific examples are stearic acid, sodiumdodecyl sulfonate surfactants, quaternary ammonium surfactants, aminoacid surfactants, betaine surfactants, fatty acid glyceride estersurfactants, fatty acid sorbitan surfactants, lecithin surfactants,and/or Tween™ series surfactants (e.g., polyethoxylated sorbitan estersurfactants, nonionic polyoxyethylene surfactants, etc.).

In some embodiments, the polymer composition may further comprisescolored materials, such as carbon black, copper phthalocyanine pigment,lead chromate, iron oxide, chromium oxide, and ultramarine blue.

In some embodiments, the polymer composition may include additionalantiviral agents other than zinc. The additional antimicrobial agentsmay be any suitable antiviral. Conventional antiviral agents are knownin the art and may be incorporated in the polymer composition as theadditional antiviral agent or agents. For example, the additionalantiviral agent may be an entry inhibitor, a reverse transcriptaseinhibitor, a DNA polymerase inhibitor, an m-RNA synthesis inhibitor, aprotease inhibitor, an integrase inhibitor, or an immunomodulator, orcombinations thereof. In some aspects, the additional antimicrobialagent or agents are added to the polymer composition.

In some embodiments, the polymer composition may include additionalantimicrobial agents other than zinc. The additional antimicrobialagents may be any suitable antimicrobial, such as silver, copper, and/orgold in metallic forms (e.g., particulates, alloys and oxides), salts(e.g., sulfates, nitrates, acetates, citrates, and chlorides) and/or inionic forms. In some aspects, further additives, e.g., additionalantimicrobial agents, are added to the polymer composition.

Exemplary Formulations

The polymer compositions described herein will be further understood bythe following exemplary formulations and embodiments.

In one embodiment, the zinc compound comprises zinc oxide, zincstearate, zinc pryithione, or zinc ammonium adipate, or combinationsthereof, the phosphorus compound comprises benzene phosphinic acid, themolar ratio of the phosphorus to the zinc ranges from 0.01:1 to 3:1, thepolymer composition has a relative viscosity of greater than 10, andfibers formed from the polymer composition demonstrate a retention rateof the zinc compound of greater than 85% when tested in a dye bath test.

In some embodiments, the antimicrobial agent, e.g., zinc, is added withthe phosphorus compound to promote the incorporation of theantimicrobial agent into the polymer matrix of the polymer composition.This procedure advantageously allows for more uniform dispersion of theantimicrobial agent throughout the eventual fiber. Further, thiscombination “builds-in” the antimicrobial within the polymer compositionto help prevent or limit the active antimicrobial ingredients from beingwashed from the fiber.

Fibers, Yarns, and Fabrics

In some cases, the hygroscopic polymers having an effective amount ofmetal ions incorporated therein may be used to prepare filament yarns.The polymer compositions impart durable antiviral properties to theresulting filament yarns that are permanent in nature and/ornear-permanent in nature.

The average fiber diameter of the hygroscopic polymers may be asufficient diameter to form a filament yarn. In some embodiments, thefilament yarn are woven or knitted into textile that may be intended foruse in next-to-skin applications, and the fibers have an average fiberdiameter less than the diameter of fibers formed for carpet-relatedapplications, which are generally unsuitable for next-to-skinapplications. For example the fibers may have an average fiber diameterless than or equal to 20 microns, e.g., less than or equal to 18microns, less than or equal to 17 microns, less than or equal to 15microns, less than or equal to 14 microns, less than or equal to 13microns, less than or equal to 12 microns. In one embodiment, at least50% of the fibers have an average fiber diameter of greater than 10microns, e.g., at least 50% of the fibers have an average fiber diameterof greater than 15 microns. The average fiber diameter may be greaterthan or equal to 1 micron, e.g., greater than 2 microns, greater than 3microns, greater than 4 microns, greater than 5 microns, greater than 6microns, greater than 7 microns, greater than 8 microns, greater than 9microns, greater than 10 microns, greater than 11 microns, greater than12 microns, or greater than 13 microns. In terms of ranges, the averagefiber diameter may be from 1 to 20 microns, e.g., from 2 to 20 microns,from 5 to 20 microns, from 7 to 20 microns, from 8 to 20 microns, from10 to 20 microns, 10 to less than 20 microns, from 10 to 19 microns, orfrom 10 to 18 microns. The distribution of fiber diameter is generallypreferred to be such that 50% of the fibers are within the range from 10to 20 microns. To the extent not indicated otherwise, test methods fordetermining average fiber diameters, may be by use of image analysisusing optical microscopes which are well known in the art.

In some aspects, the polymer composition can be processed to formantimicrobial fibers having lower denier levels. As noted above, somecarpet-related references have disclosed an antimicrobial nylon preparedin water with a zinc compound, a copper compound, and/or a phosphoruscompound. These references, however disclose higher linear denier perfilament levels (for example, greater than 12 dpf) and/or higher fiberdiameter (for example, greater than 20 microns) fibers/filaments, e.g.,carpet fibers and are not relevant to fibers/fabrics for next-to-skinend applications

As used herein, “linear denier per filament” or “dpf” refers to thenumber of filaments per deiner. In some aspects, the filament yarnhaving the antiviral properties described herein has a linear denier perfilament less than or equal to 12 dpf, e.g., less than or equal to 10dpf, less than or equal to 8 dpf, less than or equal to 6 dpf, less thanor equal to 5 dpf, less than or equal to 4 dpf, less than or equal to 3dpf, less than or equal to 2 dpf, or less than or equal to 1.5 dpf. Interms of ranges, the filament yarn having the antiviral properties has alinear denier per filament in range from 1 dpf to 12 dpf, e.g., from 1dpf to 10 dpf, from 1.1 dpf to 5 dpf, from 1.1 dpf to 3 dpf, from 1.1dpf to 2 dpf, from 1.5 dpf to 3 dpf, from 1.5 dpf to 8 dpf, from 2 dpfto 6 dpf, or from 3 dpf to 5 dpf. In terms of lower limits, theantimicrobial fiber has a denier greater than 1 dpf, e.g., greater than1.1 dpf, greater than 1.2 dpf, greater than 1.3 dpf, greater than 1.4dpf, greater than 1.5 dpf, or greater than 2 dpf.

A textile article, such as a fabric, can be made from the filament yarnhaving the antiviral properties described herein by woven or knittingtechniques. For example, fibers formed from the hygroscopic polymercomposition may be spun to form a filament yarn. The filament yarn canthen be used in knitting and/or weaving to provide textiles exhibitingthe antiviral properties of the polymer composition. Garments made fromthese textiles can withstand normal wear, and is devoid of any coated,doped, or topical treatment, which tends to abrade off during knittingand weaving. The abrasion process results in dust on machines andfabric, and lowers the effective use time of garments in normal wear andlaundering.

The textile of disclosed herein are preferably a lightweight or mediumweight fabrics. In one embodiment, the basis weight of the textile isfrom greater than or equal to 15 gsm, e.g., or greater than or equal to20 gsm, greater than or equal to 25 gsm, greater than or equal to 30gsm, greater than or equal to 35 gsm, greater than or equal to 40 gsm,greater than or equal to 45 gsm, greater than or equal to 50 gsm,greater than or equal to 75 gsm, greater than or equal to 100 gsm,greater than or equal to 125 gsm, greater than or equal to 150 gsm,greater than or equal to 175 gsm. Heavier weight textiles are generallymore durable and desired in some applications, and thus the upper rangeof the textile made of the filament yarns disclosed herein is less thanor equal to 320 gsm, e.g., less than or equal to 300 gsm, less than orequal to 250 gsm, less than or equal to 200 gsm, less than or equal to175 gsm, or less than or equal to 150 gsm. Suitable ranges of basisweight may include from 15 to 320 gsm, including subranges therein, suchas preferred ranges from 15 to 300 gsm, e.g., from 30 to 220 gsm, from35 to 200 gsm, or from 50 to 175 gsm.

The textile thickness may vary by application is generally limited bythickness that absorb excessive moisture and/or reduce air permeability.This allows a wide range from 0.05 cm to 5 cm thick textiles, e.g., from0.5 to 3 cm, from 0.1 to 2 cm, from 0.1 to 1.5 cm.

Methods of Making Fibers

In some aspects, the fibers, e.g., polyamide fibers, are made byextruding a polymer formed in a melt polymerization process. During themelt polymerization process of the polymer composition, an aqueousmonomer solution, e.g., salt solution, is heated under controlledconditions of temperature, time and pressure to evaporate water andeffect polymerization of the monomers, resulting in a polymer melt.During the melt polymerization process, sufficient amounts of a zinccompound, a copper compound, and/or a phosphorus compound are employedin the aqueous monomer solution to form the polymer composition beforepolymerization. Additional components, such as delusterants, pigments,and additional antiviral agents, may also be employed in the aqueousmonomer solution. After the metal compound, such as the preferred zinccompound and the copper compound, and/or the optional phosphoruscompound are present in the aqueous monomer solution, the polymercomposition may be polymerized. The polymerized polymer can subsequentlybe extruded into fibers. In some cases, the polymerized polymer can beextruded into other shapes, e.g., for use in preparing a high-contactproduct, as discussed below.

In some embodiments, the process for preparing an antiviral fiber (orother antiviral product) having near-permanent antiviral properties fromthe polymer composition includes preparing an aqueous monomer solution,adding a sufficient amount of metal compounds to achieve a ionconcentration of least 200 wppm. The amount of metal compounds may befrom 10 wppm to 20,000 wppm compound dispersed within the aqueousmonomer solution, and optionally adding from 0.01 wt. % to 1 wt. % ofphosphorus in a phosphorus compound, polymerizing the aqueous monomersolution to form a polymer melt, and extruding the polymer melt to forman antiviral fiber (or other antiviral product, e.g., a high-contactproduct and/or a surface layer of a high-contact product). In thisembodiment, the polymer composition comprises the resultant aqueousmonomer solution after metal (zinc) and optional phosphorus are added.In some aspects, the polymer melt can be extruded to form an antiviralfiber having a denier per filament as mentioned above.

In some embodiments, the process includes preparing an aqueous monomersolution. The aqueous monomer solution may comprise amide monomers. Insome embodiments, the concentration of monomers in the aqueous monomersolution is less than 60 wt. %, e.g., less than 58 wt. %, less than 56.5wt. %, less than 55 wt. %, less than 50 wt. %, less than 45 wt. %, lessthan 40 wt. %, less than 35 wt. %, or less than 30 wt. %. In someembodiments, the concentration of monomers in the aqueous monomersolution is greater than 20 wt. %, e.g., greater than 25 wt. %, greaterthan 30 wt. %, greater than 35 wt. %, greater than 40 wt. %, greaterthan 45 wt. %, greater than 50 wt. %, greater than 55 wt. %, or greaterthan 58 wt. %. In some embodiments, the concentration of monomers in theaqueous monomer solution is in a range from 20 wt. % to 60 wt. %, e.g.,from 25 wt. % to 58 wt. %, from 30 wt. % to 56.5 wt. %, from 35 wt. % to55 wt. %, from 40 wt. % to 50 wt. %, or from 45 wt. % to 55 wt. %. Thebalance of the aqueous monomer solution may comprise water and/oradditional additives. In some embodiments, the monomers comprise amidemonomers including a diacid and a diamine, i.e., nylon salt.

In some embodiments, the aqueous monomer solution is a salt solution.The salt solution may be formed by mixing a diamine and a diacid withwater. For example, water, diamine, and dicarboxylic acid monomer aremixed to form a salt solution, e.g., mixing adipic acid andhexamethylene diamine with water. In some embodiments, the diacid may bea dicarboxylic acid and may be selected from the group consisting ofoxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid,adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioicacid, dodecandioic acid, maleic acid, glutaconic acid, traumatic acid,and muconic acid, 1,2- or 1,3-cyclohexane dicarboxylic acids, 1,2- or1,3-phenyl enediacetic acids, 1,2- or 1,3-cyclohexane diacetic acids,isophthalic acid, terephthalic acid, 4,4′-oxybisbenzoic acid,4,4-benzophenone dicarboxylic acid, 2,6-napthalene dicarboxylic acid,p-t-butyl isophthalic acid and 2,5-furandicarboxylic acid, and mixturesthereof. In some embodiments, the diamine may be selected from the groupconsisting of ethanol diamine, trimethylene diamine, putrescine,cadaverine, hexamethyelene diamine, 2-methyl pentamethylene diamine,heptamethylene diamine, 2-methyl hexamethylene diamine, 3-methylhexamethylene diamine, 2,2-dimethyl pentamethylene diamine,octamethylene diamine, 2,5-dimethyl hexamethylene diamine, nonamethylenediamine, 2,2,4- and 2,4,4-trimethyl hexamethylene diamines,decamethylene diamine, 5-methylnonane diamine, isophorone diamine,undecamethylene diamine, dodecamethylene diamine, 2,2,7,7-tetramethyloctamethylene diamine, bis(p-aminocyclohexyl)methane,bis(aminomethyl)norbornane, C₂-C₁₆ aliphatic diamine optionallysubstituted with one or more C₁ to C₄ alkyl groups, aliphatic polyetherdiamines and furanic diamines, such as 2,5-bis(aminomethyl)furan, andmixtures thereof. In preferred embodiments, the diacid is adipic acidand the diamine is hexamethylene diamine which are polymerized to formpolyamide 6,6.

It should be understood that the concept of producing a polyamide fromdiamines and diacids also encompasses the concept of other suitablemonomers, such as, aminoacids or lactams. Without limiting the scope,examples of aminoacids can include 6-aminohaxanoic acid,7-aminoheptanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid,or combinations thereof. Without limiting the scope of the disclosure,examples of lactams can include caprolactam, enantholactam,lauryllactam, or combinations thereof. Suitable feeds for the disclosedprocess can include mixtures of diamines, diacids, aminoacids andlactams.

Of course, as noted above, polyamides are only one type of polymer thatmay be utilized in the disclosed process. In addition, otherpolymerization reactants/reactions are contemplated.

After the aqueous monomer solution is prepared, a zinc compound, acopper compound, and/or a phosphorus compound are added to the aqueousmonomer solution to form the polymer composition. In some embodiments,less than 20,000 ppm of zinc and/or less than 20,000 ppm of copper isdispersed within the aqueous monomer solution. In some aspects, furtheradditives, e.g., additional antiviral agents, are added to the aqueousmonomer solution.

In some cases, the polymer composition is polymerized using aconventional melt polymerization process. In one aspect, the aqueousmonomer solution is heated under controlled conditions of time,temperature, and pressure to evaporate water, effect polymerization ofthe monomers and provide a polymer melt. In some aspects, the use of thezinc compound, the copper compound, and/or the phosphorus compound mayadvantageously improve the relative viscosity of the polymercomposition, diminish the extraction rate of the zinc and/or coppercompound during dyeing, and, and enhance its dyeability of the resultantantiviral fiber.

In some aspects, an antiviral polyamide is prepared by a conventionalmelt polymerization of a salt. Typically, the salt solution is heatedunder pressure (e.g. 250 psig/1825×10³ n/m²) to a temperature of, forexample, about 245° C. Then the water vapor is exhausted off by reducingthe pressure to atmospheric pressure while increasing the temperatureto, for example, about 270° C. Before polymerization, the metalcompounds, preferably zinc and/or copper and, optionally, phosphorus, beadded to the salt solution. The resulting molten polymer is held at thistemperature for a period of time to bring it to equilibrium prior tobeing extruded and/or molded into a fiber or other product. In someaspects, the process may be carried out in a batch or continuousprocess.

In some embodiments, during melt polymerization, the zinc compound,e.g., zinc oxide, the copper compound, and/or the phosphorus compound,e.g., benezene phosphinic acid, are added to the aqueous monomersolution. The antiviral fiber (or other antiviral product) may comprisea polyamide that is made in a melt polymerization process and not in amaster batch process. In some aspects, the resulting fiber hasnear-permanent antiviral properties.

The antiviral agent may be added to the polyamide during meltpolymerization, and thereafter, the fiber (or other product) may beformed from extrusion and/or molding. Of course, other fiber formingmethods are also contemplated. The formed fibers may be spun to form aresultant yarn to be used in knitting and/or weaving to provide theantiviral properties in the fabrics. While polyamide may be used toexplain one aspect of the disclosure, it is understood that numerouspolymers may be used herein without deviating from the present scope ofthe disclosure.

In some embodiments, the polymer composition is extruded in order tocreate a fiber. The extrusion process itself depends on the temperatureof the mixture being sufficiently high to melt the mixture. A meltingstep may be a separate step or it may be part of either the mixingprocess or the extruding process. When the mixture is at a sufficientlyhigh temperature, the mixture may be extruded using conventionalmechanisms. The fiber may then be drawn, crimped, cut and spun into ayarn or other fabric depending on the intended end use. In someembodiments, the yarn is then dyed.

In some embodiments, the use of a multi-row die, as compared to a singlerow die, may be employed to produce the fibers/fabrics. The compositionand characteristics of the polymer compositions, e.g., RV, allow the useof multi-row dies. As such, the processes for making the fibers/fabricshave additional process benefits as a result, e.g., an increasedproduction rate, at least in part due to the properties of the polymercomposition.

Plastics

In addition to the use of the hygroscopic polymers with an effectiveamount of metal ions, and optional phosphorous, in the use of woven andknitted fabrics made also be used in plastics, such as molded plastics.In one embodiment, when used in plastics the loading of metal ions,preferably zinc ions, may be greater than or equal to 200 wppm, e.g.,greater than or equal to 300 wppm, greater than or equal to 400 wppm,greater than or equal to 500 wppm, greater than or equal to 600 wppm,greater than or equal to 700 wppm, greater than or equal to 800 wppm,greater than or equal to 900 wppm, greater than or equal to 1,000 wppm.In one embodiment, for plastic application the polymer composition maycomprises metal ions, preferably zinc ions, in an amount ranging from 5wppm to 100,000 wppm (10 wt %), e.g., 5 wppm to 20000 wppm, from 5 wppmto 17,500 wppm, from 5 wppm to 17,000 wppm, from 5 wppm to 16,500 wppm,from 5 wppm to 16,000 wppm, from 5 wppm to 15,500 wppm, from 5 wppm to15,000 wppm, from 5 wppm to 12,500 wppm, from 5 wppm to 10,000 wppm,from 5 wppm to 5000 wppm, from 5 wppm to 4000 wppm, e.g., from 5 wppm to3000 wppm, from 5 wppm to 2000 wppm, from 5 wppm to 1000 wppm, from 5wppm to 500 wppm, from 10 wppm to 20,000 wppm, from 10 wppm to 17,500wppm, from 10 wppm to 17,000 wppm, from 10 wppm to 16,500 wppm, from 10wppm to 16,000 wppm, from 10 wppm to 15,500 wppm, from 10 wppm to 15,000wppm, from 10 wppm to 12,500 wppm, from 10 wppm to 10,000 wppm, from 10wppm to 5000 wppm, from 10 wppm to 4000 wppm, from 10 wppm to 3000 wppm,from 10 wppm to 2000 wppm, from 10 wppm to 1000 wppm, from 10 wppm to500 wppm, from 50 wppm to 20,000 wppm, from 50 wppm to 17,500 wppm, from50 wppm to 17,000 wppm, from 50 wppm to 16,500 wppm, from 50 wppm to16,000 wppm, from 50 wppm to 15,500 wppm, from 50 wppm to 15,000 wppm,from 50 wppm to 12,500 wppm, from 50 wppm to 10,000 wppm, from 50 wppmto 5000 wppm, from 50 wppm to 4000 wppm, from 50 wppm to 3000 wppm, 50wppm to 500 wppm, from 100 wppm to 20,000 wppm, from 100 wppm to 17,500wppm, from 100 wppm to 17,000 wppm, from 100 wppm to 16,500 wppm, from100 wppm to 16,000 wppm, from 100 wppm to 15,500 wppm, from 100 wppm to15,000 wppm, from 100 wppm to 12,500 wppm, from 100 wppm to 10,000 wppm,from 100 wppm to 5000 wppm, from 100 wppm to 4000 wppm, from 100 wppm to500 wppm, from 200 wppm to 20,000 wppm, from 200 wppm to 17,500 wppm,from 200 wppm to 17,000 wppm, from 200 wppm to 16,500 wppm, from 200wppm to 16,000 wppm, from 200 wppm to 15,500 wppm, from 200 wppm to15,000 wppm, from 200 wppm to 12,500 wppm, from 200 wppm to 10,000 wppm,from 200 wppm to 5000 wppm, from 200 wppm to 4000 wppm, 5000 wppm to20000 wppm, from 200 wppm to 500 wppm, from 500 ppm to 10000 wppm, from1000 ppm to 7000 wppm, or from 3000 ppm to 5000 wppm.

For plastic applications, in addition to the polymer, metal ions, andoptional phosphorous, the polymer compositions may further comprisemolding additives, which are generally not employed when preparing apolymer composition for spinning and blowing methods for fiberproduction.

The polyamide compositions for plastic applications disclosed hereininclude one or more impact modifiers. The inventors have found thatthese impact modifiers beneficially can be an elastomeric or rubberymaterial selected to have good interaction and compatibility with, anddispersion among, the one or more polyamide polymers of the composition.The impact modifier can include a styrenic copolymer such as anacrylate-butadiene-styrene or a methyl methacrylate-butadiene-styrene.The impact modifier can include an acrylic polymer or a polyethylenepolymer such as a chlorinated polyethylene. In some embodiments, theimpact modifier includes an ethylene-octene copolymer. In some cases,the combination of the impact modifier and the melt stabilizers(optionally in the disclosed amounts and ratios) provides forsurprising, synergistic combinations of performance features, e.g.,tensile/flexural performance and impact resistance.

In some cases, the impact modifier comprises olefins, acrylates, oracrylics, or combinations thereof, including polymers of these compoundssuch as polyolefins or polyacrylates. These compounds may be modified,e.g., modified (grafted) with maleic anhydride. In some embodiments, theimpact modifier comprises a maleic anhydride-modified olefin, acrylate,or acrylic, or combinations thereof. In some cases, the impact modifiercomprises a modified olefin, e.g., a maleic anhydride-modified olefin.The impact modifier may comprise a maleic anhydride-modified ethyleneoctene and/or ethylene acrylate.

In some embodiments, the impact modifier has a glass transitiontemperature ranging from ranging from 0° C. to −100° C., e.g., from −5°C. to −80° C., −10° C. to −70° C., −20° C. to −60° C., or from −25° C.to −55° C. In terms of lower limits, the impact modifier may have aglass transition temperature greater than −100° C., e.g., greater than−80° C., greater than −70° C., greater than −60° C., or greater than−55° C. In terms of upper limits, the impact modifier may have a glasstransition temperature less than 0° C., e.g., less than −5° C., lessthan −10° C., less than −15° C., or less than −25° C. It is believedthat impact modifiers having such glass transition temperaturessynergistically improve energy dissipation characteristics, e.g., impactresistance. These particular impact modifiers have glass transitiontemperatures in temperature ranges that work with the disclosedpolyamides and glass fibers to achieve improved impact performance,especially in the desired temperature ranges, e.g., −10° C. to −70° C.

The concentration of the impact modifier in the polyamide compositioncan, for example, range from 3 wt % to 30 wt %, e.g., from 2 wt % to 25wt %, from 2 wt % to 20 wt %, from 5.7 wt % to 21.9 wt %, from 4.0 wt %to 15 wt %, from 5.5 wt % to 14 wt %, from 6.0 wt % to 11.5 wt %, from8.4 wt % to 24.6 wt %, from 11.1 wt % to 27.3 wt %, or from 13.8 wt % to30 wt %. In some embodiments, the concentration of the impact modifierranges from 6 wt % to 20 wt %, e.g., from 6 wt % to 14.4 wt %, from 7.4wt % to 15.8 wt %, from 8.8 wt % to 17.2 wt %, from 10.2 wt % to 18.6 wt%, or from 11.6 wt % to 20 wt %. In terms of upper limits, the impactmodifier concentration can be less than 30 wt %, e.g., less than 27.3 wt%, less than 24.6 wt %, less than 21.9 wt %, less than 20 wt %, lessthan 18.6 wt %, less than 17.2 wt %, less than 15.8 wt %, less than 15wt %, less than 14 wt %, less than 14.4 wt %, less than 13 wt %, lessthan 11.6 wt %, less than 11.5 wt %, less than 10.2 wt %, less than 8.8wt %, less than 7.4 wt %, less than 6 wt %, or less than 5.4 wt %. Interms of lower limits, the impact modifier concentration can be greaterthan 3 wt %, greater than 4.0 wt %, greater than 5.5 wt %, greater than5.4 wt %, greater than 6 wt %, greater than 7.4 wt %, greater than 8.8wt %, greater than 10.2 wt %, greater than 11.6 wt %, greater than 13 wt%, greater than 14.4 wt %, greater than 15.8 wt %, greater than 17.2 wt%, greater than 18.6 wt %, greater than 20 wt %, greater than 21.9 wt %,greater than 24.6 wt %, or greater than 27.6 wt %. Lower concentrations,e.g., less than 3 wt %, and higher concentrations, e.g., greater than 30wt %, are also contemplated.

The weight ratio of the one or more polyamide polymers to the impactmodifier in the polyamide composition can, for example, range from 0.2to 30, e.g., from 0.2 to 4, from 0.33 to 6.7, from 2 to 7, from 3 to 6,1 to 15, from 5 to 15, from 2 to 12, from 0.54 to 11, from 0.9 to 18, orfrom 1.5 to 30. In terms of upper limits, the weight ratio of the one ormore polyamide polymers to the impact modifier can be less than 30,e.g., less than 18, less than 15, less than 12, less than 11, less than7, less than 6, less than 6.7, less than 4, less than 2.4, less than1.5, less than 0.9, less than 0.54, or less than 0.33. In terms of lowerlimits, the weight ratio of the one or more polyamide polymers to theimpact modifier can be greater than 0.2, e.g., greater than 0.33,greater than 0.55, greater than 0.9, greater than 1.5, greater than 2,greater than 2.4, greater than 3, greater than 5, greater than 6.7,greater than 11, or greater than 18. Lower ratios, e.g., less than 0.2,and higher ratios, e.g., greater than 30, are also contemplated.

The one or more heat stabilizers of the polyamide composition forplastic applications can be selected to improve performance, e.g., athigher operating temperatures, of the composition without significantlynegatively affecting the strength or ductility of the material. The heatstabilizer can include, for example, hindered phenolic stabilizers,phosphite-based stabilizers, hindered amine-based stabilizers,triazine-based stabilizers, sulfur-based stabilizers, copperstabilizers, or combinations thereof.

Examples of hindered phenolic stabilizers includeN,N′-hexane-1,6-diylbis[3-(3,5-ditert-butyl-4-hydroxyphenylpropionamide)];pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate];N,N′-hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide);triethyleneglycol-bis [3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate];3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5,5]undecane;3,5-di-tert-butyl-4-hydroxybenzyl phosphonate-diethyl ester;1,3,5-trimethyl-2,4,6-tris(3,5-ditert-butyl-4-hydroxybenzyl)benzene; and1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate.

Examples of phosphite-based stabilizers include trioctyl phosphite;trilauryl phosphite; tridecyl phosphite; octyldiphenyl phosphite;trisisodecyl phosphite; phenyl diisodecyl phosphite; phenyldi(tridecyl)phosphite; diphenyl isooctyl phosphite; diphenyl isodecylphosphite; diphenyl(tridecyl)phosphite; triphenyl phosphite; tris(nonylphenyl) phosphite; tris(2,4-di-tert-butyl phenyl) phosphite;tris(2,4-di-tert-butyl-5-methyl phenyl) phosphite;tris(butoxyethyl)phosphite;4,4′-butylidene-bis(3-methyl-6-tertbutylphenyl-tetra-tridecyl)diphosphite;tetra(C₁₂- to C₁₅-mixed alkyl)-4,4′-isopropylidenediphenyl diphosphite;4,4′-isopropylidenebis(2-tert-butylphenyl)-di(nonylphenyl)phosphite;tris(biphenyl)phosphite;tetra(tridecyl)-1,1,3-tris(2-methyl-5-tertbutyl-4-hydroxyphenyl)butanediphosphite;tetra(tridecyl)-4,4′-butylidenebis(3-methyl-6-tert-butylphenyl)diphosphite;tetra(C₁- to C₁₅-mixed alkyl)-4,4′-isopropylidenediphenyl diphosphite;tris(mono-/di-mixed nonylphenyl)phosphite;4,4′-isopropylidenebis(2-tertbutylphenyl)-di(nonylphenyl)phosphite;9,10-di-hydro-9-oxa-10-phosphorphenanthrene-10-oxide;tris(3,5-di-t-butyl-4-hydroxyphenyl)phosphite;hydrogenated-4,4′-isopropylidenediphenyl polyphosphite;bis(octylphenyl)-bis(4,4′-butylidenebis(3-methyl-6-tert-butylphenyl)-1,6-hexanol diphosphite;hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butanetriphosphite; tris(4,4′-isopropylidenebis(2-tertbutylphenyl) phosphite;tris(1,3-stearoyloxyisopropyl)phosphite;2,2-methylenebis(4,6-ditert-butylphenyl)octyl phosphite;2,2-methylenebis(3-methyl-4,6-di-tert-butylphenyl)-2-ethylhexylphosphite; tetrakis(2,4-di-tert-butyl-5-methylphenyl)-4,4′-biphenylenediphosphite; and tetrakis(2,4-di-tert-butyl phenyl)-4,4′-biphenylenediphosphite.

Phosphite-based stabilizers also include pentaerythritol-type phosphitecompounds, such as2,6-di-tert-butyl-4-methylphenyl-phenyl-pentaerythritol diphosphite;2,6-di-tert-butyl-4-methylphenyl-methyl-pentaerythritol diphosphite;2,6-di-tert-butyl-4-methylphenyl-2-ethylhexyl-pentaerythritoldiphosphite; 2,6-di-tert-butyl-4-methylphenylisodecyl-pentaerythritoldiphosphite; 2,6-di-tert-butyl-4-methylphenyl-laurylpentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-isotridecyl-pentaerythritoldiphosphite; 2,6-di-tert-butyl-4-methyl phenyl-stearyl-pentaerythritoldiphosphite; 2,6-ditert-butyl-4-methyl phenyl-cyclohexyl-pentaerythritoldiphosphite; 2,6-di-tert-butyl-4-methylphenyl-benzyl-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-ethylcellosolve-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-butylcarbitol-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-octylphenyl-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-nonylphenyl-pentaerythritoldiphosphite; bis(2,6-di-tert-butyl-4-methyl phenyl)pentaerythritoldiphosphite; bis(2,6-di-tert-butyl-4-ethylphenyl)pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-2,6-di-tertbutylphenyl-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-2,4-di-tertbutylphenyl-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-2,4-di-tertoctylphenyl-pentaerythritoldiphosphite;2,6-di-tert-butyl-4-methylphenyl-2-cyclohexylphenyl-pentaerythritoldiphosphite; 2,6-di-tert-amyl-4-methylphenyl-phenyl-pentaerythritoldiphosphite; bis(2,6-di-tert-amyl-4-methylphenyl)pentaerythritoldiphosphite; and bis(2,6-di-tert-octyl-4-methylphenyl)pentaerythritoldiphosphite.

Examples of hindered amine-based stabilizers include4-acetoxy-2,2,6,6-tetra methyl piperidine;4-stearoyloxy-2,2,6,6-tetramethylpiperidine;4-acryloyloxy-2,2,6,6-tetramethylpiperidine;4-(phenylacetoxy)-2,2,6,6-tetramethylpiperidine;4-benzoyloxy-2,2,6,6-tetramethylpiperidine;4-methoxy-2,2,6,6-tetramethylpiperidine;4-stearyloxy-2,2,6,6-tetramethylpiperidine;4-cyclohexyloxy-2,2,6,6-tetra methylpiperidine;4-benzyloxy-2,2,6,6-tetramethylpiperidine;4-phenoxy-2,2,6,6-tetramethylpiperidine;4-(ethylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine;4-(cyclohexylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine;4-(phenylcarbamoyloxy)-2,2,6,6-tetramethylpiperidine;bis(2,2,6,6-tetramethyl-4-piperidyl)-carbonate;bis(2,2,6,6-tetramethyl-4-piperidyl)-oxalate;bis(2,2,6,6-tetramethyl-4-piperidyl)-malonate;bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate;bis(2,2,6,6-tetramethyl-4-piperidyl)-adipate;bis(2,2,6,6-tetramethyl-4-piperidyl)terephthalate;1,2-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-ethane;α,α′-bis(2,2,6,6-tetramethyl-4-piperidyloxy)-p-xylene;bis(2,2,6,6-tetramethyl-4-piperidyl)-tolylene-2,4-dicarbamate;bis(2,2,6,6-tetra methyl-4-piperidyl)-hexamethylene-1,6-dicarbamate;tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,5-tricarboxylate;tris(2,2,6,6-tetramethyl-4-piperidyl)-benzene-1,3,4-tricarboxylate;1-[2-{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy}butyl]-4-[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxy]2,2,6,6-tetramethylpiperidine;and a condensation product of 1,2,3,4-butanetetracarboxylic acid;1,2,2,6,6-pentamethyl-4-piperidinol; andβ,β,β′,β′-tetramethyl-3,9-[2,4,8,10-tetraoxaspiro(5,5)undecane]diethanol.

Examples of triazine-based stabilizers include2,4,6-tris(2′-hydroxy-4′-octyloxy-phenyl)-1,3,5-triazine;2-(2′-hydroxy-4′-hexyloxy-phenyl)-4,6-diphenyl-1,3,5-triazine;2-(2′-hydroxy-4′-octyloxyphenyl)-4,6-bis(2′,4-dimethylphenyl)-1,3,5-triazine;2-(2′,4′-dihydroxyphenyl)-4,6-bis(2′,4′-dimethylphenyl)-1,3,5-triazine;2,4-bis(2′-hydroxy-4′-propyloxy-phenyl)-6-(2′,4′-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4′-methylphenyl)-1,3,5-triazine;2-(2′-hydroxy-4′-dodecyloxyphenyl)-4,6-bis(2′,4′-dimethylphenyl)-1,3,5-triazine;2,4,6-tris(2′-hydroxy-4′-isopropyloxyphenyl)-1,3,5-triazine;2,4,6-tris(2′-hydroxy-4′-n-hexyloxyphenyl)-1,3,5-triazine; and2,4,6-tris(2′-hydroxy-4′-ethoxycarbonylmethoxyphenyl)-1,3,5-triazine.

Copper stabilizers include copper halides, e.g., chlorides, bromides,iodides. Copper stabilizers also can include copper cyanide, copperoxide, copper sulfate, copper phosphate, copper acetate, copperpropionate, copper benzoate, copper adipate, copper terephthalate,copper isophthalate, copper salicylate, copper nicotinate, copperstearate, and copper complex salts coordinated to a chelating amine suchas ethylenediamine and ethylenediaminetetraacetic acid.

In some embodiments, the heat stabilizers comprise a copper-containingheat stabilizer. In some embodiments, the first copper-containing heatstabilizer comprises copper, a halogen, (or a copper halide—a compoundcontaining copper and a halogen), and optionally anorganohalo-phosphorus (organobromine-phosphorus) compound. In someaspects, the first copper-containing heat stabilizer comprises a mixtureincluding copper halides, phosphates, or phosphines, or complexesthereof. In some aspects, the first copper-containing heat stabilizercomprises a complex including copper iodide, bis(triphenylphosphine),and tris(tribromoneopentyl)phosphate. Suitable first copper-containingheat stabilizers include those described in German Patent No.DE19847626, which is incorporated by reference in its entirety.

These copper halide and organohalo-phosphorus (organobromine-phosphorus)compound combinations, when added to the polyamides described herein,result in polyamide compositions that exhibit superior heat stabilitywhile also maintaining excellent electrical properties, thus making thepolyamide compositions of the present invention ideally suited for usein the electrical/electronic industries. As a further benefit, thiscombination of a copper halide and an organophosphorus compound does notdiscolor the polyamide composition. Suitable commercial (first)copper-containing heat stabilizers include BRUGGOLEN® H3386 (availablefrom Bruggemann Chemical).

In some embodiments, the polyamide composition for plastic applicationsincludes a cerium-based heat stabilizer, e.g., cerium oxide, ceriumhydrate, and/or cerium oxyhydrate.

The concentration of the heat stabilizer in the polyamide compositioncan, for example, range from 0.1 to 5 wt %, e.g., from 0.1 wt % to 1 wt%, from 0.15 wt % to 1.5 wt %, from 0.22 wt % to 2.3 wt %, from 0.1 wt %to 3 wt %, from 0.15 wt % to 1 wt %, from 0.32 wt % to 3.4 wt %, or from0.48 wt % to 5 wt %. In some embodiments, the concentration of the heatstabilizer ranges from 0.2 wt % to 0.7 wt %. In terms of upper limits,the heat stabilizer concentration can be less than 5 wt %, e.g., lessthan 3.4 wt %, less than 3 wt %, less than 2.3 wt %. less than 1.5 wt %,less than 1 wt %, less than 0.71 wt %, less than 0.48 wt %, less than0.32 wt %, less than 0.22 wt %, or less than 0.15 wt %. In terms oflower limits, the heat stabilizer concentration can be greater than 0.1wt %, e.g., greater than 0.15 wt %, greater than 0.22 wt %, greater than0.32 wt %, greater than 0.48 wt %, greater than 0.71 wt %, greater than1 wt %, greater than 1.5 wt %, greater than 2.3 wt %, or greater than3.4 wt %. Lower concentrations, e.g., less than 0.1 wt %, and higherconcentrations, e.g., greater than 5 wt %, are also contemplated.

In some embodiments, the heat stabilizer comprises copper or acopper-containing compound such as, for example, copper iodide. Aftercombining the heat stabilizer with the other polyamide compositioncomponents, the concentration of copper in the polyamide compositioncan, for example, range from 25 ppm to 700 ppm, e.g., from 25 ppm to 180ppm, from 35 ppm to 260 ppm, from 49 ppm to 360 ppm, from 68 ppm to 500ppm, or from 95 ppm to 700 ppm. In terms of upper limits, theconcentration of copper in the polyamide composition can be less than700 ppm, e.g., less than 500 ppm, less than 360 ppm, less than 260 ppm,less than 180 ppm, less than 130 ppm, less than 95 ppm, less than 68ppm, less than 49 ppm, or less than 35 ppm. In terms of lower limits,the concentration of copper in the polyamide composition can be greaterthan 25 ppm, e.g., greater than 35 ppm, greater than 49 ppm, greaterthan 68 ppm, greater than 95 ppm, greater than 130 ppm, greater than 180ppm, greater than 260 ppm, greater than 360 ppm, or greater than 500ppm. Higher concentrations, e.g., greater than 700 ppm, and lowerconcentrations, e.g., less than 25 ppm, are also contemplated.

The weight ratio of the one or more polyamides to the heat stabilizer inthe polyamide composition can, for example, range from 1 to 850, e.g.,from 1 to 57, from 2 to 110, from 3.9 to 220, from 7.6 to 430, or from15 to 850. In terms of upper limits, the weight ratio of the one or morepolyamide polymers to the heat stabilizer can be less than 850, e.g.,less than 430, less than 220, less than 110, less than 29, less than 57,less than 15, less than 7.6, less than 3.9, or less than 2. In terms oflower limits, the weight ratio of the one or more polyamide polymers tothe heat stabilizer can be greater than 1, e.g., greater than 2, greaterthan 3.9, greater than 7.6, greater than 15, greater than 29, greaterthan 57, greater than 110, greater than 220, or greater than 430. Lowerratios, e.g., less than 1, and higher ratios, e.g., greater than 850,are also contemplated.

The weight ratio of the impact modifier to the heat stabilizer in thepolyamide composition can, for example, range from 0.5 to 300, e.g.,from 0.5 to 23, from 0.95 to 44, from 1.8 to 83, from 10 to 40 from 12to 35, from 3.4 to 160, or from 6.5 to 300. In terms of upper limits,the weight ratio of the impact modifier to the heat stabilizer can beless than 300, e.g., less than 160, less than 83, less than 44, lessthan 40, less than 35, less than 23, less than 12, less than 6.5, lessthan 3.4, less than 1.8, or less than 0.95. In terms of lower limits,the weight ratio of the impact modifier to the heat stabilizer can begreater than 0.5, e.g., greater than 0.95, greater than 1.8, greaterthan 3.4, greater than 6.5, greater than 10, greater than 12, greaterthan 23, greater than 44, greater than 83, or greater than 160. Lowerratios. e.g., less than 0.5, and higher ratios, e.g., greater than 300,are also contemplated.

The polyamide composition for plastic applications can include one ormore soluble dyes such as nigrosine or solvent black 7. Theconcentration of the nigrosine in the polyamide composition can, forexample, range from 0.1 to 5 wt %, e.g., from 0.1 wt % to 1 wt %, from0.15 wt % to 1.5 wt %, from 0.22 wt % to 2.3 wt %, from 0.32 wt % to 3.4wt %, or from 0.48 wt % to 5 wt %. In some embodiments, theconcentration of the nigrosine ranges from 1 wt % to 2 wt %, e.g., from1 wt % to 1.6 wt %, from 1.1 wt % to 1.7 wt %, from 1.2 wt % to 1.8 wt%, from 1.3 wt % to 1.9 wt %, or from 1.4 wt % to 2 wt %. In terms ofupper limits, the nigrosine concentration can be less than 5 wt %, e.g.,less than 3.4 wt %, less than 2.3 wt %, less than 2 wt %, less than 1.9wt %, less than 1.8 wt %, less than 1.7 wt %, less than 1.6 wt %, lessthan 1.5 wt %, less than 1.4 wt %, less than 1.3 wt %, less than 1.2 wt%, less than 1.1 wt %, less than 1 wt %, less than 0.71 wt %, less than0.48 wt %, less than 0.32 wt %, less than 0.22 wt %, or less than 0.15wt %. In terms of lower limits, the nigrosine concentration can begreater than 0.1 wt %, e.g., greater than 0.15 wt %, greater than 0.22wt %, greater than 0.32 wt %, greater than 0.48 wt %, greater than 0.71wt %, greater than 1 wt %, greater than 1.1 wt %, greater than 1.2 wt %,greater than 1.3 wt %, greater than 1.4 wt %, greater than 1.5 wt %,greater than 1.6 wt %, greater than 1.7 wt %, greater than 1.8 wt %,greater than 1.9 wt %, greater than 2 wt %, greater than 2.3 wt %, orgreater than 3.4 wt %. Lower concentrations, e.g., less than 0.1 wt %,and higher concentrations, e.g., greater than 5 wt %, are alsocontemplated. In some cases, the nigrosine is provided in a masterbatch,and the concentration of the nigrosine in the masterbatch and in theresultant composition can be easily calculated.

The weight ratio of the one or more polyamide polymers to the nigrosinein the polyamide composition can, for example, range from 1 to 85, e.g.,from 1 to 14, from 1.6 to 22, from 2.4 to 35, from 3.8 to 55, or from5.9 to 85. In terms of upper limits, the ratio of the one or morepolyamide polymers to the nigrosine can be less than 85, e.g., less than55, less than 35, less than 22, less than 14, less than 9.2, less than5.9, less than 3.8, less than 2.4, or less than 1.6. In terms of lowerlimits, the ratio of the one or more polyamide polymers to the nigrosinecan be greater than 1, e.g., greater than 1.6, greater than 2.4, greaterthan 3.8, greater than 5.9, greater than 9.2, greater than 14, greaterthan 22, greater than 35, or greater than 55. Higher ratios, e.g.,greater than 55, and lower ratios, e.g., less than 1, are alsocontemplated.

The weight ratio of glass fiber to the nigrosine in the polyamidecomposition can, for example, range from 2 to 60, e.g., from 2 to 15,from 2.8 to 22, from 3.9 to 30, from 5.5 to 43, or from 7.8 to 60. Interms of upper limits, the ratio of glass fiber to the nigrosine can beless than 60, e.g., less than 43, less than 30, less than 22, less than15, less than 11, less than 7.8, less than 5.5, less than 3.9, or lessthan 2.8. In terms of lower limits, the ratio of glass fiber to thenigrosine can be greater than 2, e.g., greater than 2.8, greater than3.9, greater than 5.5, greater than 7.8, greater than 11, greater than15, greater than 22, greater than 30, or greater than 43. Higher ratios,e.g., greater than 60, and lower ratios, e.g., less than 2, are alsocontemplated.

The weight ratio of the heat stabilizer to the nigrosine in thepolyamide composition can, for example, range from 0.02 to 5, e.g., from0.02 to 0.55, from 0.035 to 0.95, from 0.06 to 1.7, from 0.1 to 2.9, orfrom 0.18 to 5. In terms of upper limits, the ratio of the heatstabilizer to the nigrosine can be less than 5, e.g., less than 2.9,less than 1.7, less than 0.95, less than 0.55, less than 0.32, less than0.18, less than 0.1, less than 0.06, or less than 0.035. In terms oflower limits, the ratio of the heat stabilizer to the nigrosine can begreater than 0.02, e.g., greater than 0.035, greater than 0.06, greaterthan 0.1, greater than 0.18, greater than 0.32, greater than 0.55,greater than 0.95, greater than 1.7, or greater than 2.9. Higher ratios,e.g., greater than 5, and lower ratios, e.g., less than 0.02, are alsocontemplated.

The polyamide composition can include one or more pigments such ascarbon black. The concentration of the carbon black in the polyamidecomposition can, for example, range from 0.1 to 5 wt %, e.g., from 0.1wt % to 1.05 wt %, from 0.15 wt % to 1.55 wt %, from 0.22 wt % to 2.29wt %, from 0.32 wt % to 3.38 wt %, or from 0.48 wt % to 5 wt %. In someembodiments, the concentration of the carbon black ranges from 0.2 wt %to 0.8 wt %. In terms of upper limits, the carbon black concentrationcan be less than 5 wt %, e.g., less than 3.4 wt %, less than 2.3 wt %.less than 1.5 wt %, less than 1 wt %, less than 0.71 wt %, less than0.48 wt %, less than 0.32 wt %, less than 0.22 wt %, or less than 0.15wt %. In some embodiments, the concentration of the carbon black is lessthan 3 wt %. In terms of lower limits, the carbon black concentrationcan be greater than 0.1 wt %, e.g., greater than 0.15 wt %, greater than0.22 wt %, greater than 0.32 wt %, greater than 0.48 wt %, greater than0.71 wt %, greater than 1 wt %, greater than 1.5 wt %, greater than 2.3wt %, or greater than 3.4 wt %. Lower concentrations, e.g., less than0.1 wt %, and higher concentrations, e.g., greater than 5 wt %, are alsocontemplated.

The polyamide composition for plastic applications can include one ormore melt stabilizers (lubricants). The type and relative amount of meltstabilizer can be selected to improve processing of the composition, andto contribute to the simultaneously high strength and ductility of thematerial. The concentration of the melt stabilizer in the polyamidecomposition can, for example, range from 0.05 wt % to 5 wt %, e.g., from0.05 wt % to 3 wt %, from 0.1 wt % to 0.6 wt %, from 0.2 wt % to 0.7 wt%, from 0.3 wt % to 0.8 wt %, from 0.1 wt % to 3 wt %, from 0.4 wt % to0.9 wt %, from 0.5 wt % to 1 wt %, from 0.15 wt % to 1.5 wt %, from 0.22wt % to 2.3 wt %, from 0.32 wt % to 3.4 wt %, or from 0.48 wt % to 5 wt%. In terms of upper limits, the melt stabilizer concentration can beless than 5 wt %, e.g., less than 3.4 wt %, less than 2.3 wt %. lessthan 1.5 wt %, less than 1 wt %, less than 0.9 wt %, less than 0.8 wt %,less than 0.7 wt %, less than 0.6 wt %, less than 0.5 wt %, less than0.4 wt %, less than 0.3 wt %, less than 0.2 wt %, or less than 0.1 wt %.In terms of lower limits, the melt stabilizer concentration can begreater than 0.1 wt %, e.g., greater than 0.2 wt %, greater than 0.3 w%, greater than 0.4 wt %, greater than 0.5 wt %, greater than 0.6 wt %,greater than 0.7 wt %, greater than 0.8 wt %, greater than 0.9 wt %,greater than 1 wt %, greater than 1.5 wt %, greater than 2.3 wt %, orgreater than 3.4 wt %. Lower concentrations, e.g., less than 0.1 wt %,and higher concentrations, e.g., greater than 5 wt %, are alsocontemplated.

In some embodiments, the melt stabilizer comprises a saturated fattyacid. For example the melt stabilizer may comprise stearic acid, orbehenic acid, or combinations thereof, or salts thereof. In some cases,the melt stabilizer comprises a stearate. The melt stabilizer, in somecases can include, for example, calcium stearate, aluminum distearate,zinc stearate, calcium stearate, N,N′ ethylene bis-stearamide, stearylerucamide. In some cases, the melt stabilizer comprises stearic acid. Insome cases the zinc stearate (or zinc borate (see below)) is notconsidered the zinc AM/AV compound.

In some embodiments, the melt stabilizer does not include an ioniclubricant. In addition to other performance improvements, the disclosedmelt stabilizers, also significantly improve dispersion of thecomponents in the matrix of the polymer, e.g., the dispersion of theimpact modifiers in the polyamide matrix.

In some embodiments, the melt stabilizer may be a wax. In someembodiments, the melt stabilizer consists of a wax. In some embodiments,the wax includes a fatty acid. In some embodiments, the melt stabilizerconsists of a fatty acid. In some embodiments, the wax includes asaturated fatty acid. In some embodiments, the melt stabilizer consistsof a saturated fatty acid. In some embodiments, the wax includes stearicacid, behenic acid, or salts or combinations thereof. In someembodiments, the wax consists of stearic acid, behenic acid, or salts orcombinations thereof.

In addition to other performance improvements, the disclosed meltstabilizers, also significantly improve dispersion of the components inthe matrix of the polymer, e.g., the dispersion of the impact modifiersin the polyamide matrix, which beneficially improves impact performance.

The concentration of the melt stabilizer, e.g., stearic acid or saltthereof, in the polyamide composition can, for example, range from 0.03wt % to 4 wt %, e.g., from 0.03 wt % to 0.57 wt %, from 0.05 wt % to0.92 wt %, from 0.08 wt % to 1.5 wt %, from 0.13 wt % to 2.5 wt %, orfrom 0.21 wt % to 4 wt %. In terms of upper limits, the stearic acid orsalt concentration can be less than 4 wt %, e.g., less than 2.4 wt %,less than 1.5 wt %, less than 0.92 wt %, less than 0.57 wt %, less than0.35 wt %, less than 0.21 wt %, less than 0.13 wt %, less than 0.08 wt%, or less than 0.05 wt %. In terms of lower limits, the stearic acid orsalt concentration can be greater than 0.03 wt %, e.g., greater than0.05 wt %, greater than 0.08 wt %, greater than 0.13 wt %, greater than0.21 wt %, greater than 0.35 wt %, greater than 0.57 wt %, greater than0.92 wt %, greater than 1.5 wt %, or greater than 2.5 wt %. Higherconcentrations, e.g., greater than 4 wt %, and lower concentrations,e.g., less than 0.03 wt %, are also contemplated.

The weight ratio of the impact modifier to the melt stabilizer in thepolyamide composition can, for example, range from 1 to 100, e.g., from2 to 50, from 5 to 50, from 10 to 40, from 10 to 35, from 5 to 25, from10 to 20, from 10 to 50, from 20 to 40, or from 25 to 35. In terms ofupper limits, the ratio of the impact modifier to the melt stabilizercan be less than 100, e.g., less than 75, less than 50, less than 40,less than 35, less than 25, or less than 20. In terms of lower limits,the ratio of the impact modifier to the melt stabilizer can be greaterthan 1, e.g., greater than 2, greater than 5, greater than 10, greaterthan 20, or greater than 25. Higher ratios are also contemplated.

As noted above, the combination of the impact modifier and the meltstabilizer leads to synergistic combinations of performance features.Generally, impact modifiers are known to have detrimental effects ontensile strength. For example a degradation in shear of the polymer isobserved (shear is detrimentally increased and tensile performance isadversely affected). However, when the disclosed impact modifiers andmelt stabilizers are used together, an unexpected balance is struck, themelt stabilizers reduce or eliminate the degradation. As a result,little or no loss in tensile performance is observed, while surprisinglyimpact resilience is significantly improved.

The flame retardant package for plastic applications may vary widely,and many suitable flame retardants are known. Examples of(bromine-containing) flame retardants include hexabromocyclododecane(HBCD), decabromodiphenyl oxide (DBDPO), octabromodiphenyl oxide,tetrabromobisphenol A (TBBA), bis(tribromophenoxy)ethane,bis(pentabromophenyl)ethane, tetrabromobisphenol A epoxy resin (TBBAepoxy), tetrabromobisphenol A carbonate (TBBA-PC),ethylene(bistetrabromophthal)imide (EBTBPI),ethylenebispentabromodiphenyl, tris(tribromophenoxy)triazine (TTBPTA),bis(dibromopropyl)tetrabromobisphenol A (DBP-TBBA),bis(dibromopropyl)tetrabromobisphenol S (DBP-TBBS), brominatedpolyphenylene ethers (BrPPE) (such as poly(di)bromophenylene ether,etc.), brominated polystyrenes (BrPPE) (such as polydibromostyrenes,polytribromostyrenes, crosslinked brominated polystyrenes, etc.),brominated crosslinked aromatic polymers, brominated epoxy resins,brominated phenoxy resins, brominated styrene-maleic anhydride polymers,tetrabromobisphenol S (TBBS), tris(tribromoneopentyl)phosphate (TTBNPP),polybromotrimethylphenylindan (PBPI), andtris(dibromopropyl)-isocyanurate (TDBPIC).

Halogen-based flame retardants may also be used. Conventional flameretardant synergists include, but are not limited to, antimony oxides(such as diantimony trioxide, diantimony tetroxide, diantimony pentoxideand sodium antimonate), tin oxides (such as tin monoxide and tindioxide), iron oxides (such as iron(II) oxide and γ-iron oxide), zincoxide and zinc borate. Generally, non-halogenated flame retardants areused due to a desire to avoid the potentially adverse environmentalimpact of halogenated flame retardants.

Exemplary non-halogenated flame retardants include phosphorus- ormelamine-containing flame retardants. Melamine flame retardants areknown in the art and include melamine phosphates and melamine cyanurate.Phosphate esters are especially suitable for use. Such compoundsinclude, for example, alkyl and aryl esters of phosphoric acid such astrimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctylphosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresylphosphate, cresyldiphenyl phosphate, octyldiphenyl phosphate,tri(2-ethylhexyl) phosphate, di-iso-propylphenyl phosphate, trixylenylphosphate, tris(iso-propylphenyl) phosphate, trinaphthyl phosphate,bisphenol A diphenyl phosphate, and resorcinol diphenyl phosphate.Commonly used triaryl phosphates include, for example, triphenylphosphate (TPP), cresyl diphenyl phosphate, and tricresyl phosphate.Inorganic phosphate flame retardants such as ammonium polyphosphate(which acts as an intumescent flame retardant) may also be utilized.

Phosphinate flame retardants, including those sold under the Exolit®name, such as OP1230 and OP1400 may be used in the composition describedherein. Phosphinate flame retardants may be desirable because of theiranti-corrosive nature.

The concentration of the flame retardant in the polyamide compositioncan, for example, range from 3 wt % to 30 wt %, e.g., from 2 wt % to 25wt %, from 2 wt % to 20 wt %, from 5.7 wt % to 21.9 wt %, from 4.0 wt %to 15 wt %, from 5.5 wt % to 14 wt %, from 6.0 wt % to 11.5 wt %, from8.4 wt % to 24.6 wt %, from 11.1 wt % to 27.3 wt %, or from 13.8 wt % to30 wt %. In some embodiments, the concentration of the flame retardantranges from 6 wt % to 20 wt %, e.g., from 6 wt % to 14.4 wt %, from 7.4wt % to 15.8 wt %, from 8.8 wt % to 17.2 wt %, from 10.2 wt % to 18.6 wt%, or from 11.6 wt % to 20 wt %. In terms of upper limits, the impactmodifier concentration can be less than 30 wt %, e.g., less than 27.3 wt%, less than 24.6 wt %, less than 21.9 wt %, less than 20 wt %, lessthan 18.6 wt %, less than 17.2 wt %, less than 15.8 wt %, less than 15wt %, less than 14 wt %, less than 14.4 wt %, less than 13 wt %, lessthan 11.6 wt %, less than 11.5 wt %, less than 10.2 wt %, less than 8.8wt %, less than 7.4 wt %, less than 6 wt %, or less than 5.4 wt %. Interms of lower limits, the flame retardant concentration can be greaterthan 3 wt %, greater than 4.0 wt %, greater than 5.5 wt %, greater than5.4 wt %, greater than 6 wt %, greater than 7.4 wt %, greater than 8.8wt %, greater than 10.2 wt %, greater than 11.6 wt %, greater than 13 wt%, greater than 14.4 wt %, greater than 15.8 wt %, greater than 17.2 wt%, greater than 18.6 wt %, greater than 20 wt %, greater than 21.9 wt %,greater than 24.6 wt %, or greater than 27.6 wt %. Lower concentrations,e.g., less than 3 wt %, and higher concentrations, e.g., greater than 30wt %, are also contemplated.

In cases where the flame retardant is a non-halogenated flame retardant,the non-halogenated flame retardant may be present in an amount of atleast 5 wt. %, based on the total weight of the composition, e.g., atleast 7.5 wt. %, at least 10 wt. %, or at least 12.5 wt. %. In terms ofupper limits, the non-halogenated flame retardant is present in anamount of less than 25 wt. %, e.g., less than 22.5 wt. %, less than 20wt. %, or less than 17.5 wt. %. In terms of ranges, the non-halogenatedflame retardant is present from 5 to 25 wt. %, e.g., from 7.5 to 22.5wt. %, from 10 to 20 wt. %, or from 12.5 to 17.5 wt. %.

The polyamide composition for plastic applications can also include oneor more chain terminators, viscosity modifiers, plasticizers, e.g.,diundecyl phthalate, UV stabilizers, catalysts, other polymers,delusterants, antimicrobial agents, antistatic agents, opticalbrighteners, extenders, processing aids, talc, mica, gypsum,wollastonite and other commonly used additives known to those of skillin the art. Additional suitable additives may be found in PlasticsAdditives, An A-Z reference, Edited by Geoffrey Pritchard (1998). Theoptional addition of a stabilizer to the additive dispersion is presentin an exemplary embodiment. Stabilizers suitable for the additivedispersion include, but are not limited to, polyethoxylates (such as thepolyethoxylated alkyl phenol Triton X-100), polypropoxylates, blockcopolymeric polyethers, long chain alcohols, polyalcohols, alkylsulfates, alkyl-sulfonates, alkyl-benzenesulfonates, alkylphosphates,alkyl-phosphonates, alkyl-naphthalene sulfonates, carboxylic acids andperfluoronates.

In some embodiments, the stain resistance of the polyamide compositioncan be improved by salt-blending the polyamide precursor with a cationicdye modifier, such as 5-sulfoisophthalic acid or salts or otherderivatives thereof.

Chain extenders can also be included in the polyamide composition.Suitable chain extender compounds include bis-N-acyl bislactamcompounds, isophthaloyl bis-caprolactam (IBC), adipoyl bis-caprolactam(ABC), terphthaloyl bis-caprolactam (TBS), and mixtures thereof.

The polyamide composition for plastic applications can also includeanti-block agents. Inorganic solids, usually in the form of diatomaceousearth, represent one class of materials that can be added to thedisclosed polyamide composition. Non-limiting examples include calciumcarbonate, silicon dioxide, magnesium silicate, sodium silicate,aluminum silicate, aluminum potassium silicate, and silicon dioxide areexamples of suitable antiblock agents.

The polyamide compositions for plastic applications can also include anucleating agent to further improve clarity and oxygen barrier as wellas enhance oxygen barrier. Typically, these agents are insoluble, highmelting point species that provide a surface for crystallite initiation.By incorporating a nucleating agent, more crystals are initiated, whichare smaller in nature. More crystallites or higher % crystallinitycorrelates to more reinforcement/higher tensile strength and a moretortuous path for oxygen flux (increased barrier); smaller crystallitesdecreases light scattering which correlates to improved clarity.Non-limiting examples include calcium fluoride, calcium carbonate, talcand Nylon 2,2.

The polyamide compositions for plastic applications can also includeorganic anti-oxidants in the form of hindered phenols such as, but notlimited to, Irganox 1010, Irganox 1076 and Irganox 1098; organicphosphites such as, but not limited to, Irgafos 168 and Ultranox 626;aromatic amines, metal salts from Groups IB, IIB, III, and IV of theperiodic table and metal halides of alkali and alkaline earth metals.

The polyamide composition for plastic applications includes areinforcing filler, e.g., glass fiber. The glass fiber can include sodalime silicate, zirconium silicates, calcium borosilicates,alumina-calcium borosilicates, calcium aluminosilicates, magnesiumaluminosilicates, or combinations thereof. The glass fiber can includelong fibers, e.g., greater than 6 mm, short fibers, e.g., less than 6mm, or combinations thereof. The glass fiber can be milled.

The amount of glass fiber in the polyamide composition relative to theamounts of the other composition components can be selected toadvantageously provide additional strength without negatively affectingmaterial ductility. The concentration of glass fiber in the polyamidecomposition can, for example, range from 10 wt % to 60 wt %, e.g., from10 wt % to 40 wt %, from 15 wt % to 45 wt %, from 20 wt % to 50 wt %,from 25 wt % to 55 wt %, or from 30 wt % to 60 wt %. In someembodiments, the concentration of glass fiber ranges from 25 wt % to 40wt % e.g., from 25 wt % to 34 wt %, from 26.5 wt % to 35.5 wt %, from 28wt % to 37 wt %, from 29.5 wt % to 38.5 wt %, or from 31 wt % to 40 wt%. In certain aspects, the concentration of glass fiber ranges from 30wt % to 35 wt %. In terms of upper limits, the glass fiber concentrationcan be less than 60 wt %, e.g., less than 55 wt %, less than 50 wt %,less than 45 wt %, less than 40 wt %, less than 38.5 wt %, less than 37wt %, less than 35.5 wt %, less than 34 wt %, less than 32.5 wt %, lessthan 31 wt %, less than 29.5 wt %, less than 28 wt %, less than 26.5 wt%, less than 25 wt %, less than 20 wt %, or less than 15 wt %. In termsof lower limits, the glass fiber concentration can be greater than 10 wt%, e.g., greater than 15 wt %, greater than 20 wt %, greater than 25 wt%, greater than 26.5 wt %, greater than 28 wt %, greater than 29.5 wt %,greater than 31 wt %, greater than 32.5 wt %, greater than 34 wt %,greater than 35.5 wt %, greater than 37 wt %, greater than 38.5 wt %,greater than 40 wt %, greater than 45 wt %, greater than 50 wt %, orgreater than 55 wt %. Lower concentrations, e.g., less than 10 wt %, andhigher concentrations, e.g., greater than 60 wt %, are alsocontemplated.

Additional details regarding formulations for molded products aredisclosed in concurrently filed US non-provisional application entitled“Antimicrobial/Antiviral Plastics and molded Products” [attorney docketno. 07101-APM (497528)], which is incorporated herein by reference.

Applications

The present disclosure related to various applications of the antiviralpolymer compositions and the fibers, fabrics, and textiles formedtherefrom. As described above, these products demonstrate permanent,e.g., near-permanent, antiviral properties. Thus, the polymercomposition can be incorporated into any of a variety of products forwhich prolonged protection from viral infection and/or pathogenesis maybe desirable.

In some aspects, a medical product or device may be prepared using thepolymer compositions described herein. In some embodiments, for example,a medical product or device may be prepared from fibers, yarns, orfabrics formed from the polymer composition.

Because the fibers and/or textile exhibit durable antiviral propertiesthat are permanent in nature or near-permanent in nature, the medicalproduct or device may also exhibit permanent, e.g., near-permanentantiviral properties. Thus, in some cases, the medical product or devicemay be reusable.

Examples of medical products or devices that can be prepared using thepolymer compositions include masks, wipes, gowns, towels, protectiveclothing, or protect nets.

For example, the polymer composition may be used in the preparation of amask, e.g., a surgical mask, a procedure mask, a medical mask, and/or adust mask, having antiviral properties. The antiviral properties of themask may be particular useful in protecting against the transmissionand/or infection of a virus, e.g., between and/or among healthcareworkers or members of a larger population. The structure of the mask isnot particularly limited, and any known structure may be used.Preferably, the mask is designed so as to ensure adequate protection(e.g., against transmission) while providing for wearer comfort andbreathability. In some cases, the mask comprises a number of layers,e.g., one or more layers, two or more layers, or three or more layers.In some embodiments, one or more layers of the mask may be formed by awoven or knitted fabric according the present disclosure. In someaspects, the mask further comprises one or more layers of an antiviralfabric (as disclosed herein) in combination with one or more layers ofanother antiviral polymer layer that may be woven, knitted or nonwoven.

By way of another example, the polymer composition may be used in thepreparation of a filter, e.g., an air filter, a HEPA filter, anautomotive cabin air filter, or an aircraft air filter. The antiviralproperties of the filter may be particular useful in protecting againstthe transmission and/or infection of a virus, e.g., by air flow units(such as HVAC). The structure of the filter is not particularly limited,and any known structure may be used. Preferably, the filter is designedso as to ensure adequate protection (e.g., against transmission) whileproviding for appropriate permeability. In some cases, the filtercomprises a number of layers, e.g., one or more layers, two or morelayers, or three or more layers. In some embodiments, one or more layersof the filter may be formed by an woven or knitted fabric according thepresent disclosure.

By way a more general example, the polymer composition may be used inthe preparation of a layered structure, which may have any of a varietyof uses. The layered structure may comprise, for example, an antivirallayer comprising a described polymer composition as well as anadditional layer. The incorporation of the polymer composition into thelayered structure provides the layered structure with antiviralproperties, such as limiting, reducing, or inhibiting infection and/orpathogenesis of a virus. In some cases, the layered structure mayinclude an additional antiviral agent, optionally comprising an entryinhibitor, a reverse transcriptase inhibitor, a DNA polymeraseinhibitor, an m-RNA synthesis inhibitor, a protease inhibitor, anintegrase inhibitor, or an immunomodulator, or combinations thereof. Insome cases, the layer structure includes a fabric of nanofibers producedfrom the polymer composition. In some cases, the layer structureincludes a woven or knitted polymer structure produced from the polymercomposition.

Those skilled in the art will appreciate that fibers, yarns, fabrics,and textile polymer structures exhibiting antiviral properties may bedesirably incorporated into other products, such as textiles, for any ofa variety of uses.

High-Contact Products

The polymer composition may be used in the preparation of a high-contactproduct. A high-contact product may be any product that is handled(e.g., touched) by a user or otherwise comes into contact with the userduring conventional use. The polymer compositions may be utilized forhigh-contact products used in any setting.

In some embodiments, a disclosed polymer composition alone is used toprepare a high-contact product. Said another way, a high-contact productmay be entirely composed of a polymer composition. In some embodiments,a disclosed polymer composition is a component of the high contactproduct. For example, the polymer composition may form a layer (e.g., asurface coating) on the high-contact product.

As discussed above, the polymer compositions described hereindemonstrate antiviral properties, and these properties may besurprisingly enhanced by certain characteristics of the polymercomposition. For example, the use of a hydrophilic and/or hygroscopicpolymer improves (e.g., increases) the antiviral activity of the polymercomposition. Thus, the polymer compositions may be especially useful forhigh-contact products that come into contact with moisture duringtypical use. For example, the polymer compositions may be especiallyuseful for masks (e.g., medical masks) and air filters (e.g., HVACfilters, automobile filters, aviation filters).

Methods of making the high-contact product are not particularly limited,and conventional methods may be used. In some embodiments, for example,a hot melt polymerization (e.g., as discussed above with respect tofibers) may be used to prepare the polymer composition, which may thenbe extruded and/or formed into the high-contact product.

The following examples are illustrative and should not be read aslimiting the definition of a high-contact product.

In some cases, the high-contact product may be a piece or portion offurniture, e.g., for use in an academic, business, or medical setting.For example, the polymer composition may be used in the preparation of achair (e.g., as a part or all of a chair base, a chair handle, a chairseatback, or a chair leg), a table (e.g., as a part or all of a tabletopor a table leg), a desk (e.g., as a part or all of a desktop or a deskleg), shelving, or a bed (e.g., as a part or all of a bedframe, a bedrailing, a bed leg, a headboard, or a footboard).

In some cases, the high-contact product may be a piece or portion of aconsumer product, e.g., consumer electronics. For example, the polymercomposition may be used in the preparation of a housing or case for acellular phone, a component of computer (e.g., a housing, a display, akeyboard, or a mouse of a desktop computer or a laptop computer), acomponent of a kitchen or culinary item (e.g., a refrigerator, oven,stove, range, microwave oven, cookware, or cooking utensil), or acomponent of a personal hygiene product (e.g., a toothbrush, hair brush,comb, toilet seat, toilet seat cover, razor, or an air filter).

In some cases, the high-contact product may be a piece or portion ofmedical equipment. For example, the polymer composition may be used inthe preparation of monitor equipment (e.g., a blood pressure monitor oran ultrasound probe), radiology equipment (e.g., a portion of an MRImachine or a CT machine), a ventilator, or a patient transfer sheet.

In some cases, the high-contact product may be a piece or portion of atextile product. For example, the polymer composition may be used in thepreparation of clothing, a medical gown, a medical mask, a medicaldrape, a patient transfer slip sheet, curtains, bedding (e.g.,bedsheets, a duvet, a duvet cover, a pillow, or a pillow cover), orluggage (e.g., a suitcase or a garment bag), shoes (e.g., a shoe upper,a shoe lining, or sewing thread for a shoe).

In some cases, the high-contact product may be a molded article. Forexample, the polymer composition may be used in the preparation ofpackaging (e.g., disposable or reusable food and/or liquid packaging),automotive parts or components, mechanical parts, toys, musicalinstruments, furniture, or storage containers.

As noted above, the polymer of the polymer composition are capable ofabsorbing moisture, and generally referred to as being hydrophilicand/or hygroscopic. This may be particularly beneficial for certainhigh-contact products, which may be exposed to moisture duringoperation. Moisture (e.g., moisture present on the skin, in sweat, or insaliva) typically facilitates viral transmission, and a hydrophilicand/or hygroscopic polymer composition may draw in virus-containingmoisture. In particular, the moisture may be attracted to thecomposition (e.g., on a surface of the high-contact product), and thecomposition may then kill a virus contained therein. Thus, the disclosedpolymer compositions may be used in forming (in whole or in part)high-contact products that greatly reduce transmission of a virus.

It will be appreciated that variants of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be combined intomany other different systems or applications. Various presentlyunforeseen or unanticipated alternatives, modifications, variations orimprovements therein may be subsequently made by those skilled in theart which are also intended to be encompassed by the following claims orthe equivalents thereof.

EXAMPLES Example 1—Hygroscopic Polymer Absorption of Viruses

This experiment demonstrates that hygroscopic polymers retain virus andthe virus is not trapped on the surface. A knitted polyamide 66 (PA66)textile having a basis weight of 186 gsm was used a hygroscopic polymer.The moisture absorption was greater than 0.3% based on the weight of thepolymer. For purposes of this example the metal ions and/or compoundswere not loaded and the cytotoxicity was not measured.

Moreover, the strong absorbing properties of cotton may constitute apotential health hazard if cotton face masks are not washed or disposedof properly.

IAV strain A/WSN/33 (H1N1) was added to a textile PA66 fabric. After a30-min incubation at room temperature, the fabric was washed with PBS toremove unabsorbed virus and all liquid removed. To estimate the amountof remaining liquid, the sample tube with fabric was weighed andcompared to its dry weight.

A similar test was repeated for International Antimicrobial Council(IAC) issued cotton fabric, and polypropylene (PPP) fabric from adisposable type II 3-ply face mask. Cotton is hydrophilic by hassignificant moisture absorption of up to 500%, while polypropylene ishydrophobic.

The PA66 fabric retained significantly more liquid than polypropylene,both relative to the applied volume and weight of the fabric, as shownin FIG. 1A, and the normalized dry weight, as shown in FIG. 1B.Subsequent analysis of the IAV titer in the input and fabric washesshowed that the cotton and PA66 fabrics readily absorbed the appliedvirus, respectively, while less virus was observed by the polypropylenefabric as shown in FIG. 1C. As noted herein, this ability to absorb ofthe virus beneficially contributes to the AM/AV properties of thefibers/fabrics. Detrimentally, the exceedingly strong absorbingproperties of cotton may constitute a potential health hazard if cottonface masks are not washed or disposed of properly.

In order to remove H1N1 from the cotton and PA66 fabrics withoutinactivating the virus, different concentrations of polysorbate-80(tween-80)—a mild detergent that is also used in IAV vaccinepreparations—were added to the PBS wash buffer. It was found that 0.05%tween-80 succeeded in recovering more than 94% of the virus from thePA66 fabric, whereas 61% was removed from the cotton fabric. Nocytopathic effects of the detergent on the MDCK cells used for theplaque assay were observed, but the presence of 0.05%-0.1% tween-80increased the apparent viral titer relative to infections in PBS (seeFIG. 1D and FIG. 1E), whereas 0.25-0.5% tween-80 reduced IAV WSN plaquesize, and 1% tween-80 prevented viral infection entirely.

To confirm whether other viruses could be removed from PA66 fabric, theexperiment was repeated with SARS-CoV-2 for each of the materials. Itwas found that over 92% of SARS-CoV-2 can be recovered from the wovenPA66 fabric using 0.05% tween-80, while up to 59% could be recoveredfrom the cotton fabric.

Together, these results demonstrate that IAV and SARS-CoV-2 are stronglyabsorbed by the PA66 fabric, suggesting that these materials would traprespiratory viruses inside the textile, which in turn provides forunexpectedly improved AM/AV performance. At the same time, thesefindings demonstrate that polypropylene, with its low hygroscopy, ispoor at trapping respiratory viruses. Since IAV and SARS-CoV-2 can beremoved from a PA66 fabric with a mild detergent, this protocol can beuseful for testing the inactivating properties of other hygroscopicfabrics.

It was found that the addition of tween-80 results in efficient virusrelease from PA66, but not as much from cotton. Virus retention onpolypropylene, which is used for the construction of disposable 3-plymasks, is poor, in line with its hydrophobic properties. This resultimplies that respiratory viruses remain on the surface of polypropylenematerials. Together with findings that SARS-CoV-2 can survive on varioussurfaces for several hours to days, and even 7 days onpolypropylene-based surgical face masks, this implies that non-absorbentfabrics, such as polypropylene 3-ply masks, may present potential healthhazards.

TABLE 1 Polymer Absorption of Viruses PA 66 Fabric Cotton PolypropyleneMoisture absorption Hygroscopic Hydrophilic/ Hydrophobic HygroscopicLiquid retention  1.9  4.1   0.01 (μl/μl) FIG. 1A Liquid retention (dry 1.75  2.8   0.1 basis) FIG. 1B (μl/mg) Virus retention (H1N1)  0.04 0.05   0.005 (%/mg) FIG. 1C Virus recovery @ 0.05 94% 61% <0.01Tween-80 (H1N1) (%) FIG. 1D Virus recovery @ 0.05 92% 59% <0.01 Tween-80(SARS-CoV-2) (%) FIG. 1E

Example 2—Virus Inactivation

Copper and zinc surfaces or particles have been found to inactivate IAVstrains and seasonal CoV HCoV 229E. Other polymers, such aspolypropylene imbued with copper oxide can potentially inactive IAV.However, in this example, it was demonstrated that embedding zinc intopolymers has additional unexpected benefits versus copper. For example,zinc has a much higher propensity to ionize than copper, and therebyprovides a much faster reaction potential. Moreover, zinc oxide, whichwas embedded in the PA66 polymer used in this example, is considered aGenerally Regarded As Safe (GRAS) compound by the FDA, which canadvantageously speed up the development and regulation process. Finally,zinc has been found to not cause discoloration of the polymer or fabric,which enables much broader applicability.

However, like copper, zinc ions are cytotoxic in tissue culture (seeFIG. 2A), which confounds analysis of their effect on viral titers. Itwas surprisingly found that addition of an equimolar concentration ofEDTA after the virus incubation with zinc ions can, beneficially,efficiently chelate zinc and preventing cytotoxic effects (see FIG. 2B).EDTA alone does not have any cytotoxic effects itself or reduce theviral titer (see FIG. 2A). A Western blot IAV HA and NP protein levelsafter exposure to zinc chloride and neutralization with EDTA is shown inFIG. 2C, as detected with LI-COR. FIG. 2E is a graph of the NA segmentRT-qPCR analysis of IAV virus after exposure to zinc chloride andneutralization with EDTA. In these figures, an asterisk indicatesp-value, with *=p<0.05, **=p<0.005 and ns=p>0.05.

To investigate if zinc ions can directly inactivate IAV, influenza viruswas incubated with varying concentrations of zinc chloride. After 60min, the reactions were stopped with an equimolar amount of EDTA andsubsequently diluted for virus titer determination by plaque assay. Asshown in FIG. 2E, a reduction of approximately 2-log on the IAV titer byzinc chloride was observed. To gain more insight into the mechanism ofvirus inactivation, viral protein levels were analyzed by western blot.For IAV, it was found that in the presence of zinc chloride HA levelswere reduced in a concentration-dependent manner, while NP levels didnot diminish as shown in FIG. 2D. To test if IAV RNA levels wereaffected, a 120-nt long spike RNA was added to each sample, viral RNAwas extracted, and reverse transcriptions was performed using a 3′terminal NA primer. cDNA levels were next quantified using qPCR of theNA gene-encoding segment. No effect of zinc chloride on viral NA segmentlevels was found. Together, these results indicate that zinc ions caninactivate an IAV (H1N1) strain by destabilization of the viral surfaceproteins.

The above results show that zinc ions, as disclosed and describedherein, can directly inactivate an IAV H1N1 strain. And, EDTA canefficiently chelate zinc ions in solution and prevent any false positivevirus inactivation when testing.

Example 3—Deactivation of Virus in Fabrics

In the following examples, the hygroscopic polymer used was polyamide 66from Ascend Performance Materials and the zinc ion was added using zincammonium adipate obtained from Microban. The polymer was formed intofilament yarn and knitted into different fabrics for testing.Unprocessed and dyed fabrics were tested. The polymers tested are shownin Table 2. A comparative example using having no zinc was also tested.

TABLE 2 Basis Fiber Zinc Ion Weight Diameter Example Polymer Processed(wppm) (gsm) (microns) 3-A PA 6,6 Dyed 328 186 11 3-B PA 6,6 Dyed 328186 11 3-C PA 6,6   447 157 11 3-D PA 6,6   447 157 11 3-E PA 6,6 Greige375 157 11 3-F PA 6,6 Greige 500 157 11 Comparative PA 6,6    0 132 11Example A

The antiviral efficacy was determined using ISO 18184(Textiles-Determination of antiviral activity of textile products—2019)testing that was modified to include SARS-CoV-2. The antiviral effectwas demonstrated using different types of virus, namely OC43 humancoronavirus, H1N1, and SARS-CoV-2.

To investigate the robustness and saturation level of the inactivationby fabrics containing embedded zinc oxide, the fabrics were standardizedby weight. The viral load was varied and added to each fabric over arange of 10³ to 10⁷ pfu. The liquid volume applied to each fabric waskept constant. After incubation for different periods of time (0, 5, 20,60 and 120 minutes), fabrics were washed with PBSTE and virus titersestimated by plaque assay or focal forming assay. Example 3-A was testedfor H1N1, and SARS-CoV-2 as shown in the virus reduction (pfu/ml) inFIG. 3A.

For testing SARS-CoV-2 a modified ISO 18184:2019 was used for Examples3-A, 3-B and Comparative Example A. The neutralization broth was aSCDLPTE broth that was soya casein digest lecithin polysorbate brothwith 0.5% tween-80 and 10 mM EDTA.

For Examples 3-A and 3-B, three samples of 0.4 grams of fabric wereplaced flat in a 10 cm Petri dish, respectively. Next, 200 μl of virusinoculum was added to each Test Article and exposed for 30 sec, 5 min,20 min, 60 min, or 120 min. Next, the Test Article was transferred to a50 ml tube. Then 1800 μl of SCDLPTE was added to the Test Article andthe tube extensively vortexed. Finally, 1 ml of SCDLPTE and virus wereremoved from the 50 ml tube and transferred to an Eppendorf tube forplaque assay.

For Comparative Example A, one sample of 0.4 grams of fabric was placedflat in a 10 cm Petri dish. Next, 200 μl of virus inoculum was added tothe Control Article and exposed for 5 min or 120 min. Next, the ControlArticle was transferred to a 50 ml tube. Then 1800 μl of SCDLPTE wasadded to the Control Article and the tube extensively vortexed. Finally,approximately 2 ml of SCDLPTE and virus were removed from the 50 ml tubeand transferred to an Eppendorf tube for plaque assay.

Plaque or TCID50 assays were performed with samples from 6.1 and 6.2.Plaque assays were performed on Vero E6 cells with 250 ul of 10-folddilutions (100 to 10-3) of viral suspension (or no virus control) for 60min at room temperature. Plaque assays were incubated for 2 days at 37°C. Cells were fixed in 4% formaldehyde and stained with Chrystal Violet.Plaque forming units (PFU) were counted to determine infectious viraltiters (PFU/ml).

As shown, Example 3-A demonstrates the effect on the reduction rate ofIAV, HCov OC43, and SARS-CoV-2 titer after exposure. Data points wereobtained by from time courses experiments in which viral load was variedand subsequently estimated the maximum reduction rate (exponentialphase) for each time course. Reduction was normalized topfu·gram⁻¹·min⁻¹ using the dry fabric weight. IAV, HCov OC43, andSARS-CoV-2 data points were fit with a linear line and no difference wasobserved between the fits as shown in FIG. 3B. R² for IAV fit is shown.Together, these results suggest that IAV and coronaviruses areefficiently inactivated by fabrics containing embedded zinc ions.

FIG. 3C is a Western blot analysis of IAV HA and NP protein levels afterexposure of IAV to the fabric of Example 3-A and comparative example A.Both the virus that was removed (eluate) from each fabric with PBSTE aswell as the virus that remained on each fabric was analyzed and reportedin FIG. 3D. Similarly, a Western blot analysis of SARS-CoV-2 S and Nprotein levels after exposure of virus to the Example 3-A andcomparative example A as shown in FIG. 3E. Both the virus that wasremoved (eluate) from each fabric with PBSTE as well as the virus thatremained on each fabric were analyzed and reported in FIG. 3F.

Additional results for the fabrics of Table 2 are reported in Table 3using similar tests. The results were taken after 20 or 60 minutes.

TABLE 3 ISO 18184- OC43-Human ISO 18184 ISO 18184 Example CoronavirusH1N1-Influenza SARS-CoV-2 20 mins 60 mins 20 mins 60 mins 60 mins 60mins 3-A  1.77  4.15  1.23 3-B  1.77  4.15  2.61 3-C  5.27  2.49 3-D 1.57  2.79 3-E  1.55  2.19 3-F  4.88  2.19 Comparative  0.11  0.37 0.24  0.39 Example A

RT-qPCR analysis of the viral RNA showed no significant reduction inviral RNA integrity after treatment with zinc (or copper). By contrast,analysis of the stability of the viral surface and capsid proteinsrevealed a reduced stability of the virus surface proteins HA and S, forIAV and SARS-CoV-2, respectively, after exposure to zinc and aberrantmigration of these proteins after exposure to copper ions. There was noeffect on the viral nucleoprotein, which allowed use of the viralnucleoprotein as internal control. A similar altered surface protein tonucleoprotein ratio on the zinc-embedded PA66 fabrics was observed.Together, these results suggest that the reduction in virus titer afterexposure to the zinc ions derives from inactivation of the viral surfaceproteins.

Example 4—Durability of Filament Yarns

To investigate if fabrics constructed from fibers containing zinc oxidemaintain their zinc oxide content after washing, a PA66 fabric with 500ppm zinc oxide was washed 25 or 50 times using the standardized homelaundry test protocol AATCC M6-2016. Subsequent analysis of the zincoxide (zinc ion) content after washing revealed that zinc remainedpresent in fabrics for up to 50 washes (see FIGS. 4A and 4B). Analysisof the reduction in IAV titer on these fabrics demonstrated only a minorreduction in reduction, suggesting that these fabrics are suitable forreuse.

A sample of a hygroscopic polymer, (PA66) having a zinc ionconcentration of 488 wppm with a basis weight of 147 gsm and an averagefiber diameter of 11 microns was repeatedly wash to demonstrate theretention and durable anti-viral characteristics. The knit was an H7120interlock. The testing was done after 1, 25, and 50 washes and theresults shown in FIGS. 4A and 4B are also captured in Table 4.

TABLE 4 ISO 18184- ISO 18184 ISO 18184 Zinc OC43-Human H1N1- SARS- # ofion Zinc Coronavirus Influenza CoV-2 washes (wppm) retention (60 mins)(60 mins) (60 mins) Initial 488 — 6.32 3.23 1.04  1x 522 >99% 2.81 1.922.11 25x 499 >99% 6.16 2.74 1.96 50x 505 >99% 3.46 2.29 1.66

EMBODIMENTS

As used below, any reference to a series of embodiments is to beunderstood as a reference to each of those embodiments disjunctively(e.g., “Embodiments 1-4” is to be understood as “Embodiments 1, 2, 3, or4”).

Embodiment 1 is an antiviral article comprising a textile having a basisweight of greater than or equal to 15 gsm, the textile comprisingfilament yarn comprising one or more hygroscopic polymers each having anaverage fiber diameter from 1 to 20 microns; and one or more metal ionsincorporated within the one or more hygroscopic polymers fordeactivating viruses exposed to the article, wherein the concentrationof the one or more metal ions is greater than or equal to 200 wppm.

Embodiment 2 is an antiviral article of Embodiment 1 wherein the one ormore hygroscopic polymers comprise a polyamide, polyurethane,polycarbonate, polyesters, polyacrylates, or acrylonitrile butadienestyrene.

Embodiment 3 is an antiviral article comprising a textile having a basisweight of greater than or equal to 15 gsm, the textile comprisingfilament yarn comprising polyamide having an average fiber diameter from1 to 20 microns; and one or more metal ions incorporated within the oneor more polyamide for deactivating viruses exposed to the article,wherein the concentration of the one or more metal ions is greater thanor equal to 200 wppm.

Embodiment 4 is an antiviral article according to Embodiments 2, 3, or4, wherein the polyamide is the reaction product of at least one C₄ toC₁₆ aliphatic dicarboxylic acid, cyclo dicarboxylic acid, or aromaticdicarboxylic acid and at least one alkylene diamine having from 2 to 16carbon atoms or an aromatic diamine.

Embodiment 5 is an antiviral article according to any of the previousembodiments wherein the fabric as a basis weight from 15 to 320 gsm,e.g., from 15 to 300 gsm, e.g., from 30 to 220 gsm, from 35 to 200 gsm,or from 50 to 175 gsm.

Embodiment 6 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 2 to 20 microns.

Embodiment 7 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 5 to 20 microns.

Embodiment 8 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 7 to 20 microns.

Embodiment 9 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 8 to 20 microns.

Embodiment 10 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 10 to 20 microns.

Embodiment 11 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 10 to 19 microns.

Embodiment 12 is an antiviral article according to any of the previousembodiments wherein the one or more hygroscopic polymers each have anaverage fiber diameter from 10 to 18 microns.

Embodiment 13 is an antiviral article according to any of the previousembodiments wherein the metal ions comprise zinc ions, copper ions, orsilver ions.

Embodiment 14 is an antiviral article according to any of the previousembodiments wherein the metal ions comprise zinc ions.

Embodiment 15 is an antiviral article according to any of the previousembodiments wherein the concentration of the one or more metal ions isfrom 200 wppm to 1,000 wppm.

Embodiment 16 is an antiviral article according to any of the previousembodiments further comprising one or more metal compounds, and the oneor more metal compounds comprise oxides, carbonates, stearates,pyrithiones, or adipates.

Embodiment 17 is an antiviral article according to any of the previousembodiments wherein the concentration of the one or more metal ionsexceeds the concentration of one or more metal compounds.

Embodiment 18 is an antiviral article according to any of the previousembodiments wherein the one or more metal ions incorporated within theone or more hygroscopic polymers for deactivating viruses exposed to thearticle, wherein the virus is an adenovirus, a herpesvirus, a poxvirus,a rhinovirus, a coxsackievirus, an enterovirus, a morbillivirus, acoronavirus, an influenza A virus, an avian influenza virus, aswine-origin influenza virus, or an equine influence virus.

Embodiment 19 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 1-log reduction ofhuman coronavirus after a period of 60 minutes according to ISO18184:2019.

Embodiment 20 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 2-log reduction ofhuman coronavirus after a period of 60 minutes according to ISO18184:2019.

Embodiment 21 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 3-log reduction ofhuman coronavirus after a period of 60 minutes according to ISO18184:2019.

Embodiment 22 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 1-log reduction ofH1N1 after a period of 60 minutes according to ISO 18184:2019.

Embodiment 23 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 2-log reduction ofH1N1 after a period of 60 minutes according to ISO 18184:2019.

Embodiment 24 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 3-log reduction ofH1N1 after a period of 60 minutes according to ISO 18184:2019.

Embodiment 25 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 1-log reduction ofSars-CoV-2 after a period of 60 minutes according to ISO 18184:2019.

Embodiment 26 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 2-log reduction ofSars-CoV-2 after a period of 60 minutes according to ISO 18184:2019.

Embodiment 27 is an antiviral article according to any of the previousembodiments wherein the article exhibits at least a 3-log reduction ofSars-CoV-2 after a period of 60 minutes according to ISO 18184:2019.

Embodiment 28 is an antiviral article according to any of the previousembodiments wherein the filament yarn further comprises an phosphoruscompound and wherein the phosphorus compound comprises benzenephosphinic acid, phosphorous acid, or manganese hypophosphite, orcombinations thereof.

Embodiment 29 is an antiviral article according to any of the previousembodiments wherein the article is reusable.

Embodiment 30 is an antiviral article according to any of the previousembodiments wherein the article has a metal ion retention rate ofgreater than or equal to 65%.

Embodiment 31 is an antiviral article according to any of the previousembodiments wherein the article comprises a mask, wipe, gown, towel,protective clothing, or protective net.

Embodiment 32 is an antiviral article according to any of the previousembodiments wherein the textile is woven.

Embodiment 33 is an antiviral article according to any of the previousembodiments wherein the textile is knitted.

Embodiment 34 is an antiviral article according to any of the previousembodiments the filament yarn comprises linear denier per filament (dpf)less than or equal to 12 dpf.

Embodiment 35 is an antiviral article according to any of the previousembodiments the filament yarn comprises linear denier per filament (dpf)from 1 dpf to 12 dpf.

Embodiment 36 is an antiviral article according to any of the previousembodiments the filament yarn comprises linear denier per filament (dpf)from 1 dpf to 10 dpf.

Embodiment 37 is an antiviral filament yarn comprising one or morehygroscopic polymers each having an average fiber diameter from 1 to 20microns and one or more metal ions incorporated within the one or morehygroscopic polymers for deactivating viruses exposed to the yarn,wherein the concentration of the one or more metal ions is greater thanor equal to 200 wppm; and wherein the filament yarn is woven or knittedinto a textile.

Embodiment 38 is an antiviral filament yarn according to Embodiment 37,wherein the filament yarn comprises linear denier per filament (dpf)less than or equal to 12 dpf.

Embodiment 39 is an antiviral filament yarn according to Embodiment 37,wherein the filament yarn comprises linear denier per filament (dpf)from 1 dpf to 12 dpf.

Embodiment 40 is an antiviral article according to Embodiment 37,wherein the filament yarn comprises linear denier per filament (dpf)from 1 dpf to 10 dpf.

Embodiment 41 is an antiviral filament yarn of Embodiments 37-40 whereinthe one or more hygroscopic polymers comprise a polyamide, polyurethane,polycarbonate, polyesters, polyacrylates, or acrylonitrile butadienestyrene.

Embodiment 42 is an antiviral filament yarn according to Embodiment 41,wherein the polyamide is the reaction product of at least one C₄ to C₁₆aliphatic dicarboxylic acid, cyclo dicarboxylic acid, or aromaticdicarboxylic acid and at least one alkylene diamine having from 2 to 16carbon atoms or an aromatic diamine.

Embodiment 43 is an antiviral filament yarn according to Embodiments37-42, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 2 to 20 microns.

Embodiment 44 is an antiviral filament yarn according to Embodiments37-43, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 5 to 20 microns.

Embodiment 45 is an antiviral filament yarn according to Embodiments37-44, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 7 to 20 microns.

Embodiment 46 is an antiviral filament yarn according to Embodiments37-45, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 8 to 20 microns.

Embodiment 47 is an antiviral filament yarn according to Embodiments37-46, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 10 to 20 microns.

Embodiment 48 is an antiviral filament yarn according to Embodiments37-47, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 10 to 19 microns.

Embodiment 49 is an antiviral filament yarn according to Embodiments37-48, wherein the one or more hygroscopic polymers each have an averagefiber diameter from 10 to 18 microns.

Embodiment 50 is an antiviral filament yarn according to Embodiments37-49, wherein the metal ions comprise zinc ions, copper ions, or silverions.

Embodiment 51 is an antiviral filament yarn according to Embodiments37-50, wherein the metal ions comprise zinc ions.

Embodiment 52 is an antiviral filament yarn according to Embodiments37-51, wherein the concentration of the one or more metal ions is from200 wppm to 1,000 wppm.

Embodiment 53 is an antiviral filament yarn according to Embodiments37-52, further comprising one or more metal compounds, and the one ormore metal compounds comprise oxides, carbonates, stearates,pyrithiones, or adipates.

Embodiment 54 is an antiviral filament yarn according to Embodiments37-53, wherein the concentration of the one or more metal ions exceedsthe concentration of one or more metal compounds.

Embodiment 55 is an antiviral filament yarn according to Embodiments37-54, wherein the article has a metal ion retention rate of greaterthan or equal to 65%.

We claim:
 1. An antiviral article comprising: a textile having a basisweight of greater than or equal to 15 gsm, the textile comprisingfilament yarn comprising: one or more hygroscopic polymers each havingan average fiber diameter from 1 to 20 microns; and one or more metalions incorporated within the one or more hygroscopic polymers fordeactivating viruses exposed to the article, wherein the concentrationof the one or more metal ions is greater than or equal to 200 wppm. 2.The article of claim 1, wherein the one or more hygroscopic polymerscomprise a polyamide, polyurethane, polycarbonate, polyesters,polyacrylates, or acrylonitrile butadiene styrene.
 3. The article ofclaim 2, wherein the polyamide is the reaction product of at least oneC₄ to C₁₆ aliphatic dicarboxylic acid, cyclo dicarboxylic acid, oraromatic dicarboxylic acid and at least one alkylene diamine having from2 to 16 carbon atoms or an aromatic diamine.
 4. The article of claim 1,wherein the one or more hygroscopic polymers absorbs more than 0.3% ofmoisture based on the weight of the one or more hygroscopic polymers. 5.The article of claim 1, wherein the fabric as a basis weight from 15 to320 gsm.
 6. The article of claim 1, wherein the one or more hygroscopicpolymers each have an average fiber diameter from 10 to 20 microns. 7.The article of claim 1, wherein the metal ions comprise zinc ions,copper ions, or silver ions.
 8. The article of claim 1, wherein theconcentration of the one or more metal ions is from 200 wppm to 1,000wppm.
 9. The article of claim 1, wherein the article exhibits at least a1-log reduction of human coronavirus after a period of 60 minutesaccording to ISO 18184:2019.
 10. The article of claim 1, wherein thearticle exhibits at least a 1-log reduction of H1N1 after a period of 60minutes according to ISO 18184:2019.
 11. The article of claim 1, whereinthe article exhibits at least a 1-log reduction of Sars-CoV-2 virusafter a period of 60 minutes according to ISO 18184:2019.
 12. Thearticle of claim 1, further comprising one or more metal compounds, andthe one or more metal compounds comprise oxides, carbonates, stearates,pyrithiones, or adipates.
 13. The article of claim 12, wherein theconcentration of the one or more metal ions exceeds the concentration ofone or more metal compounds.
 14. The article of claim 1, wherein thearticle is reusable.
 15. The article of claim 1, wherein the filamentyarn further comprises an phosphorus compound and wherein the phosphoruscompound comprises benzene phosphinic acid, phosphorous acid, ormanganese hypophosphite, or combinations thereof.
 16. The article ofclaim 15, wherein the metal ion is a zinc ion and wherein the molarratio of the phosphorus to the zinc ranges from 0.01:1 to 3:1.
 17. Thearticle of claim 1, wherein the article has a metal ion retention rateof greater than or equal to 65%.
 18. The article of claim 1, wherein thearticle comprises a mask, wipe, gown, towel, protective clothing, orprotective net.
 19. The article of claim 1, wherein the virus is anadenovirus, a herpesvirus, a poxvirus, a rhinovirus, a coxsackievirus,an enterovirus, a morbillivirus, a coronavirus, an influenza A virus, anavian influenza virus, a swine-origin influenza virus, or an equineinfluence virus.
 20. An antiviral filament yarn comprising: one or morehygroscopic polymers each having an average fiber diameter from 1 to 20microns; and one or more metal ions incorporated within the one or morehygroscopic polymers for deactivating viruses exposed to the yarn,wherein the concentration of the one or more metal ions is greater thanor equal to 200 wppm; and wherein the filament yarn is woven or knittedinto a textile.